CN104822691A - Transition-metal free reductive cleavage of aromatic C-O, C-N, and C-S bonds by activated silanes - Google Patents

Transition-metal free reductive cleavage of aromatic C-O, C-N, and C-S bonds by activated silanes Download PDF

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CN104822691A
CN104822691A CN201380063061.6A CN201380063061A CN104822691A CN 104822691 A CN104822691 A CN 104822691A CN 201380063061 A CN201380063061 A CN 201380063061A CN 104822691 A CN104822691 A CN 104822691A
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CN104822691B (en
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R·H·格鲁布斯
亚历克斯·费多罗夫
安东·陶拓夫
尼古拉斯·A·斯韦什尔
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California Institute of Technology CalTech
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    • C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
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    • C07C209/28—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with other reducing agents
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    • C07C209/62—Preparation of compounds containing amino groups bound to a carbon skeleton by cleaving carbon-to-nitrogen, sulfur-to-nitrogen, or phosphorus-to-nitrogen bonds, e.g. hydrolysis of amides, N-dealkylation of amines or quaternary ammonium compounds
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    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
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    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
    • C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
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    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
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    • C07F7/0803—Compounds with Si-C or Si-Si linkages
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    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C07F7/0814—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring is substituted at a C ring atom by Si
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Abstract

The present invention describes chemical systems and methods for reducing C-O, C-N, and C-S bonds, said system comprising a mixture of (a) at least one organosilane and (b) at least one strong base, said system being substantially free of a transition-metal compound, and said system optionally comprising at least one molecular hydrogen donor compound, molecular hydrogen, or both.

Description

By reactive silane to the C-O key of aromatics, C-N key and C-S key without transition metal reductive cleavage
The cross reference of related application
This application claims the U.S. Patent application the 61/708th submitted on October 2nd, 2012, No. 931 and on May 2nd, 2013 submit to U.S. Patent application the 61/818th, the right of priority of No. 573, for all objects, the content of each of these applications is incorporated to its entirety by reference.
Technical field
The present invention relates to the material that processing derives from biomass, this material comprises biomass (such as, xylogen, sugar), biomass liquefying thing (biomass liquifaction), biological pyrolysis oil, black liquor, coal, gelatin liquefaction thing, Sweet natural gas or petroleum technology stream.Especially, the present invention relates to for aromatic substance is such as found in this type of process flow those in the system and way of C-O key, C-N key and C-S key reductive cleavage (reductive cleaving).
Background
In the past few decades, to the demand of the growth of energy together with the fossil fuel reserves successively decreased for effectively manufacturing fuel from reproducible Biological resources and bulk chemicals creates great growth in interest.Natural heterobiopolymer xylogen has developed into the major objective of cost-effective Wood Adhesives from Biomass, because the aromatic oxide structural unit repeated can provide the product of high energy content and the potential use to the useful derivative applied for fine chemistry.But at present, the use of xylogen is limited clearly, because current technology does not allow effectively to resolve into its composition structural unit with required selectivity.One of significant challenge relevant to this technique is the demand to making dissimilar strong aromatic series C-O key (Fig. 1) reductive cleavage be present in xylogen, and this is also the problem relevant to liquidation of coal.
When reconstructed coal and petroleum products in the face of other challenge, wherein cumulative environmental planning requires to eliminate sulphur substantially from feedstream.The burning of sulphur creates oxysulfide, and this oxysulfide itself is not only unexpected in environment, and tends to pollute the noble metal catalyst such as used in catalyst.To not only making biomass depolymerization, and there is large interest for the technology of the sulphur reducing or eliminating the remnants from these raw material matrixes.
According to both economic point of view and environment viewpoint, known Ni catalyzer provides the selective reduction relating to aryl-oxygen key to transform (selective reductive transformation), but only with the carrying capacity of 5-20%, and the use of Ni and other transition-metal catalysts is problematic at these levels.In addition, this type of catalyzer is not reported as about C-N or C-S key is useful.And, although having the general method for aromatics C-O bond cleavage solution not adopting nickel or other transition-metal catalysts will be useful, but the unique known selectable method at relatively low temperatures for the ether-splitting solution without metal depends on excessive basic metal or electrocatalysis technique, these techniques are tended to be high cost, unsustainable and unpractical.
The present invention relates at least some in addressing these problems.
General introduction
Various embodiments of the present invention provide for reducing the chemical system of C-O key, C-N key and C-S key, every individual system comprises the mixture of (a) at least one organosilane and (b) at least one highly basic, described system substantially without transistion metal compound, and described system optionally comprise at least one molecular hydrogen donor compound, molecular hydrogen or the two.
Other embodiments provide the method for the C-X key in reduction organic substrate (organic substrate), wherein X is O, N or S, often kind of method comprises: be enough to reduce a certain amount of matrix C-X key at least partially condition under, make the described matrix comprising at least one C-O key, C-N key or C-S key of described amount and comprise the chemical system of (a) at least one organosilane with the mixture of (b) at least one highly basic and contact; Wherein said chemical system substantially without transistion metal compound, and described chemical system optionally comprise at least one molecular hydrogen donor compound, molecular hydrogen or the two.
Accompanying drawing is sketched
When read in conjunction with the accompanying drawings, understanding of the application further.For the object illustrating theme, the exemplary of theme shown in the drawings; But theme disclosed herein is not limited to disclosed concrete method, device and system.In addition, accompanying drawing is not necessarily drawn in proportion.In the accompanying drawings:
Figure 1A and Figure 1B shows the example being such as present in C-O key in hardwood xylogen.Fig. 1 C shows some in the model compound discussed for the C-O bonding of key in this application.
Fig. 2 show as in embodiment 5.8 describe, diphenylene-oxide, Et 3the EPR spectrum of SiH and KOt-Bu reaction mixture in toluene.Identical signal is observed when not adding diphenylene-oxide.
The detailed description of illustrative embodiment
The present invention builds in series reaction, each of these reactions depends on the simple mixtures of organosilane and highly basic, they form the in-situ reducing gonosome system (its structures and characteristics remains completely unknown) of the C-O key that can activate in liquid phase, C-N key and C-S key together, and without the need to there is transition-metal catalyst, UV radiation or electric discharge.These reactions with develop for impressive progress that the feedstream based on biomass is resolved in aromatic raw material and fuel practical approach relevant.Importantly, this reaction has large interest, because it only creates environment friendly silicon hydrochlorate as by product and avoids toxic metal waste streams, to observe utilizing the nearly all additive method proposed in document as in order to this object.When sulphur compound, two C-S activation protocol is observed under such reaction conditions, and this reaction conditions causes sulphur atom to remove from the form of substrate molecule.This significant observation is also relevant to the desulfurization of the sulfurous pollutants in the crude stream with large interest and high value.
The present invention more easily can understand by referring to combining drawings and Examples whole forming a part of this disclosure and the following description carried out.Should understand; the invention is not restricted to described herein or that illustrate concrete product, method, conditioned disjunction parameter, and term used herein only by the mode of example for describing the object of specific embodiments and being not intended to be the restriction of any claimed invention.Similarly, unless otherwise expressly specified, otherwise about for improvement of effect or the possible mechanism of reason or any description of pattern mean it is only illustrative, and invention is herein by any mechanism of this type of suggestion of the effect that is not used to improve or reason or the correct or incorrect constraint of pattern.Run through herein, recognize, this description refers to the method for the described composition of composition and manufacture and use.In other words; if the disclosure describes or claimed with composition or manufacture or the feature using the method for composition to be associated or embodiment; so it will be appreciated that this description or claim intention make these features or embodiment extend in these contexts each in embodiment (i.e. composition, manufacture method and using method).
In the disclosure, singulative " (a) ", " one (an) " and " being somebody's turn to do (the) " comprise plural thing, and comprise at least this occurrence to referring to of concrete numerical value, clearly indicate unless context separately has.Therefore, such as, be referring at least one in this type of material well known by persons skilled in the art and equivalent thereof to referring to of " a kind of material ", etc.
On duty by use descriptor " about " be represented as approximation time, should be understood that this occurrence forms another embodiment.Generally speaking, the use of term " about " instruction approximation, this approximation can be depended on the expected performance sought by being obtained by disclosed theme and changes and the function used wherein based on this theme in the concrete context of this theme understood.Those skilled in the art can make this terminological interpretation be regular content.In some cases, the number for the significant figure of occurrence can be the degree non-limiting method determining word " about ".In other cases, the grade used in a series of value may be used for determining desired extent, and this desired extent is available for the term " about " of each value.If existed, so all scopes comprise end points and are capable of being combined.In other words, refer to the value stated in scope each value be included within the scope of this.
It will be appreciated that for the sake of clarity, some feature of the present invention described in the context of independent embodiment in this article also can provide in single embodiment with being combined.In other words, unless not compatible or get rid of particularly significantly, otherwise each single embodiment is considered to be capable of being combined with any other embodiment and this combination is considered to another embodiment.On the contrary, for simplicity, the of the present invention various feature described in the context of single embodiment also can be provided separately or is provided so that any subgroup is incompatible.Finally, although embodiment can the part of the part being described to series of steps or more universal architecture, each described step also can be considered to capable of being combined self the independently embodiment with other embodiments.
Transitional term " comprises ", " substantially by ... composition " and " by ... composition " is intended to comprise their the received meaning in patent jargon; That is, (i) and " comprising ", " containing " or " with ... be feature " " comprising " of synonym comprise end points or open and do not get rid of other, unreferenced key element or method steps; (ii) " by ... composition " get rid of key element, step or the composition of not specifying in the claims; And (iii) scope of claim to be limited to the material or step of specifying and not to affect in fact the foundation characteristic of claimed invention and the material of novel feature or step by " substantially by ... composition ".Phrase " comprise " (or its equivalent) in described by embodiment be also provided in " by ... composition " and " substantially by ... form " aspect describe independently those as embodiment.For those embodiments that provide of aspect " substantially by ... composition ", foundation characteristic and novel feature are methods (or the system used in these class methods or from its derivative composition) as the operability without transition metal method of reductive cleavage affecting C-O key, C-N key or C-S key.
When presenting list, unless otherwise directed, otherwise should be understood that each single key element of this list and each combination of this list are independent embodiments.Such as, the list being rendered as the embodiment of " A, B or C " should be interpreted as comprising embodiment " A ", " B ", " C ", " A or B ", " A or C ", " B or C " or " A, B or C ".
Run through this specification sheets, their the normal meaning will be provided for word, as the skilled person will appreciate.But in order to avoid misreading, the meaning of some term will be defined or is illustrated especially.
Term as used herein " alkyl " be commonly referred to as straight chain, side chain or the stable hydrocarbon group of ring-type, but not necessarily containing 1 to about 24 carbon atom, preferably containing 1 to about 12 carbon atom, such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, octyl group, decyl and similar group, and cycloalkyl such as cyclopentyl, cyclohexyl and similar group.Usually, but not necessarily, the alkyl of this paper contains 1 to about 12 carbon atom.Term " low alkyl group " means 1 alkyl to 6 carbon atoms, and particular term " cycloalkyl " means usually to have 4 to 8, preferably 5 to the alkyl of the ring-type of 7 carbon atoms.Term " alkyl of replacement " refers to the alkyl replaced by one or more substituting group group, and term " containing heteroatomic alkyl " and " assorted alkyl " refer to the alkyl that wherein at least one carbon atom is replaced by heteroatoms.If do not indicated in addition, so term " alkyl " and " low alkyl group " comprise respectively straight chain, side chain, ring-type, unsubstituted, replace and/or containing heteroatomic alkyl and low alkyl group.
Term as used herein " alkylidene group " refer to dual functional straight chain, side chain or the alkyl of ring-type, wherein " alkyl " as hereinbefore defined.
Term as used herein " thiazolinyl " refer to containing at least one double bond 2 straight chains to about 24 carbon atoms, side chain or the alkyl of ring-type, such as vinyl, positive propenyl, pseudoallyl, n-butene base, isobutenyl, octenyl, decene base, tetradecene base, hexadecylene base, icosa alkene base, two tetradecene bases and similar group.Preferred thiazolinyl contains 2 to about 12 carbon atoms herein.Term " low-grade alkenyl " means 2 thiazolinyls to 6 carbon atoms, and particular term " cycloalkenyl group " means preferably have 5 thiazolinyls to the ring-type of 8 carbon atoms.Term " thiazolinyl of replacement " refers to the thiazolinyl replaced by one or more substituting group group, and term " containing heteroatomic thiazolinyl " and " assorted thiazolinyl " refer to the thiazolinyl that wherein at least one carbon atom is replaced by heteroatoms.If do not indicated in addition, so term " thiazolinyl " and " low-grade alkenyl " comprise respectively straight chain, side chain, ring-type, unsubstituted, replace and/or containing heteroatomic thiazolinyl and low-grade alkenyl.
Term as used herein " alkenylene " refer to dual functional straight chain, side chain or the thiazolinyl of ring-type, wherein " thiazolinyl " as hereinbefore defined.
Alkyl that is that term as used herein " alkynyl " refers to containing at least one triple bond 2 straight chains to about 24 carbon atoms or side chain, such as ethynyl, positive proyl and similar group.Preferred alkynyl contains 2 to about 12 carbon atoms herein.Term " low-grade alkynyl " means 2 alkynyls to 6 carbon atoms.Term " alkynyl of replacement " refers to the alkynyl replaced by one or more substituting group group, and term " containing heteroatomic alkynyl " and " assorted alkynyl " refer to the alkynyl that wherein at least one carbon atom is replaced by heteroatoms.If do not indicated in addition, so term " alkynyl " and " low-grade alkynyl " comprise respectively straight chain, side chain, unsubstituted, replace and/or containing heteroatomic alkynyl and low-grade alkynyl.
Term as used herein " alkoxyl group " means the alkyl combined by independent, terminal ether bonding; That is, " alkoxyl group " group can be expressed as-O-alkyl, and wherein alkyl is as defined above." lower alkoxy " group means containing 1 alkoxyl group to 6 carbon atoms.Similarly, " alkene oxygen base " and " rudimentary alkene oxygen base " refers to the thiazolinyl and low-grade alkenyl that are combined by independent, terminal ether bonding respectively, and " alkynyloxy group " and " lower alkynyloxy " refers to respectively by alkynyl that is independent, the combination of terminal ether bonding and low-grade alkynyl.
Term " aromatics " refers to the loop section of the H ü ckel 4n+2 rule meeting aromaticity, and comprise aryl (namely, carbocyclic ring) structure and heteroaryl (being also referred to as heteroaromatic) both structures, these structures comprise the part of aryl, aralkyl, alkaryl, heteroaryl, heteroaralkyl or alkane heteroaryl.
Term as used herein " aryl ", and unless otherwise specified, otherwise refer to containing single aromatic ring or condense together, the aromatic substituent of multiple aromatic rings of (making different aromatic rings be incorporated into shared group such as methylene moiety or ethylene moieties) connected directly or indirectly or structure.Unless otherwise modification, otherwise term " aryl " refers to carbocyclic ring structure.Preferred aryl contains 5 to 24 carbon atoms, and particularly preferred aryl contains 5 to 14 carbon atoms.Exemplary aryl contains an aromatic ring or two aromatic rings that are that condense or connection, such as, and phenyl, naphthyl, xenyl, diphenyl ether, pentanoic, benzophenone and similar group." aryl of replacement " refers to the aryl moiety replaced by one or more substituting group group, and term " containing heteroatomic aryl " and " heteroaryl " refer to the aryl substituent that wherein at least one carbon atom is replaced by heteroatoms, as will be described in more detail below in.
Term as used herein " aryloxy " refers to the aryl combined by independent, terminal ether bonding, and wherein " aryl " is as defined above." aryloxy " group can be expressed as-O-aryl, and wherein aryl is as defined above.Preferred aryloxy contains 5 to 24 carbon atoms, and particularly preferred aryloxy contains 5 to 14 carbon atoms.The example of aryloxy includes but not limited to phenoxy group, o-halo-phenoxy, m-halo-phenoxy, p-halo-phenoxy, o-Difluoro-phenoxy, m-Difluoro-phenoxy, p-Difluoro-phenoxy, 2,4-Dimethoxv-phenoxy, 3,4,5-trimethoxy-phenoxy and similar group.
Term " alkaryl " refers to the aryl with alkyl substituent, and term " aralkyl " refers to the alkyl with aryl substituent, and wherein " aryl " and " alkyl " is as defined above.Preferred alkaryl and aralkyl contain 6 to 24 carbon atoms, and particularly preferred alkaryl and aralkyl contain 6 to 16 carbon atoms.Alkaryl comprises, such as, and p-aminomethyl phenyl, 2,4-3,5-dimethylphenyls, p-cyclohexyl phenyl, 2,7-dimethyl naphthyls, 7-ring octyl group naphthyl, 3-ethyl-ring penta-Isosorbide-5-Nitrae-diene and similar group.The example of aralkyl includes but not limited to benzyl, 2-phenyl-ethyl group, 3-phenyl-propyl group, 4-phenyl-butyl, 5-phenyl-pentyl, 4-phenylcyclohexyl, 4-benzyl rings hexyl, 4-phenylcyclohexyl methyl, 4-benzylcyclohexylmethyl and similar group.Term " aryloxy alkyl " and " aralkoxy " refer to the substituting group of formula-OR, and wherein R is alkaryl as just defined or aralkyl respectively.
Term " acyl group " refers to the substituting group with formula-(CO)-alkyl ,-(CO)-aryl or-(CO)-aralkyl; and term " acyloxy " refers to the substituting group with formula-O (CO)-alkyl ,-O (CO)-aryl or-O (CO)-aralkyl, wherein " alkyl ", " aryl " and " aralkyl " are as hereinbefore defined.
Term " ring-type " and " ring " refer to alicyclic group or aromatic group, and these groups maybe can cannot be substituted and/or be containing heteroatomic, and can be monocycle, dicyclo or many rings.Term " alicyclic " is used in reference to aliphatic circular part in the meaning of routine, as contrary with aromatic circular part, and can be monocycle, dicyclo or many rings.Term " acyclic " refers to wherein double bond maybe can cannot be comprised in the structure in ring structure.
Term " halo ", " halogenide " and " halogen " are used in reference to the substituting group of chlorine, bromine, fluorine or iodine in the meaning of routine.
" alkyl " refers to containing 1 to about 30 carbon atom, preferably 1 to about 24 carbon atom, most preferably 1 to the univalent hydrocarbyl group of about 12 carbon atoms, comprise straight chain, side chain, ring-type, saturated such as, with undersaturated material, alkyl, thiazolinyl, aryl and similar group.Term " lower alkyl " means 1 to 6 carbon atom, preferably 1 alkyl to 4 carbon atoms, and term " alkylene " means the divalent hydrocarbon moiety containing 1 to about 30 carbon atom, preferably 1 to about 24 carbon atom, most preferably 1 extremely about 12 carbon atoms, comprise straight chain, side chain, ring-type, saturated with undersaturated material.Term " lower alkylene " means 1 alkylene to 6 carbon atoms." alkyl of replacement " refers to the alkyl replaced by one or more substituting group group, and term " containing heteroatomic alkyl " and " assorted alkyl " refer to the alkyl that wherein at least one carbon atom is replaced by heteroatoms.Similarly, " alkylene of replacement " refers to the alkylene replaced by one or more substituting group group, and term " containing heteroatomic alkylene " and " assorted alkylene " refer to the alkylene that wherein at least one carbon atom is replaced by heteroatoms.Except as otherwise noted, otherwise term " alkyl " and " alkylene " should be interpreted as respectively comprising replacement and/or containing heteroatomic hydrocarbyl portion and alkylene moiety.
As the term " containing heteroatomic " in " containing heteroatomic alkyl " refer to one of them or more the hydrocarbon molecule that replaced by the atom outside de-carbon such as nitrogen, oxygen, sulphur, phosphorus or silicon, normally nitrogen, oxygen or sulfo-of carbon atom or hydrocarbyl molecular fragment.Similarly, term " assorted alkyl " refers to containing heteroatomic alkyl substituent, term " heterocycle " refers to containing heteroatomic cyclic substituents, and term " heteroaryl " and " heteroaromatic " refer to respectively containing heteroatomic " aryl " and " aromatics " substituting group and similar group.It should be noted that " heterocycle " group or compound can be or can not be aromatics, and " heterocycle " can be monocycle, dicyclo or many rings in addition, as described about term " aryl " above.The alkyl that example comprises alkoxy aryl, alkyl alkylthio base (alkylsulfanyl) replaces of assorted alkyl, the alkylating aminoalkyl group of N-and similar group.The example of heteroaryl substituent comprises pyrryl, pyrrolidyl, pyridyl, quinolyl, indyl, pyrimidyl, imidazolyl, 1,2,4-triazolyl, tetrazyl, etc., and be pyrrolidyl, morpholinyl, piperazinyl, piperidyl containing the example of heteroatomic alicyclic group, etc.
As what mention in some in definition mentioned above, at least one hydrogen atom meaning to be bonded in alkyl, alkyl, aryl or other parts carbon (or other) atom as " replacement " in " alkyl of replacement ", " alkyl of replacement ", " aryl of replacement " and analogue is replaced by one or more non-hydrogen substituent.This type of substituent example includes but not limited to: the functional group being called as " Fn " herein, such as halogen, hydroxyl, sulfhydryl, C 1-C 24Alkoxyl, C 2-C 24Alkene oxygen base, C 2-C 24Alkynyloxy group, C 5-C 24Aryloxy group, C 6-C 24Aralkoxy, C 6-C 24Aryloxy alkyl, acyl group (comprise C 1-C 24Alkyl-carbonyl (-CO-alkyl) and C 6-C 24Aryl carbonyl (-CO-aryl)), (-O-acyl group, comprises C to acyloxy 2-C 24Alkyl-carbonyl oxygen (-O-CO-alkyl) and C 6-C 24Aryl carbonyl oxygen (-O-CO-aryl)), C 2-C 24Alkoxy carbonyl ((CO)-O-alkyl), C 6-C 24Aryloxycarbonyl (-(CO)-O-aryl), halo carbonyl ((-CO)-X, wherein X is halogen), C 2-C 24Alkylcarbonate (-O-(CO)-O-alkyl), C 6-C 24Arylcarbonic acid root (-O-(CO)-O-aryl), carboxyl (-COOH), carboxylate radical (-COO-), carbamoyl (-(CO)-NH 2), list-(C 1-C 24Alkyl) carbamoyl (-(CO) NH (C that replaces 1-C 24Alkyl)), two-(C 1-C 24Alkyl) carbamoyl (-(CO)-N (C that replaces 1-C 24Alkyl) 2), list-(C 1-C 24Haloalkyl) carbamoyl (-(CO)-NH (C that replaces 1-C 24Alkyl)), two-(C 1-C 24Haloalkyl) carbamoyl (-(CO)-N (C that replaces 1-C 24Alkyl) 2), list-(C 5-C 24Aryl) replace carbamoyl (-(CO)-NH-aryl), two-(C 5-C 24Aryl) carbamoyl (-(CO)-N (C that replaces 5-C 24Aryl) 2), two-N-(C 1-C 24Alkyl), N-(C 5-C 24Aryl) replace carbamoyl, thiocarbamoyl (-(CS)-NH 2), list-(C 1-C 24Alkyl) thiocarbamoyl (-(CO)-NH (C that replaces 1-C 24Alkyl)), two-(C 1-C 24Alkyl) thiocarbamoyl (-(CO)-N (C that replaces 1-C 24Alkyl) 2), list-(C 5-C 24Aryl) replace thiocarbamoyl (-(CO)-NH-aryl), two-(C 5-C 24Aryl) thiocarbamoyl (-(CO)-N (C that replaces 5-C 24Aryl) 2), two-N-(C 1-C 24Alkyl), N-(C 5-C 24Aryl) replace thiocarbamoyl, urea groups (-NH-(CO)-NH 2), cyano group (-C ≡ N), cyanate radical (-O-C=N), thiocyanate radical (-S-C=N), formoxyl (-(CO)-H), thioformyl (-(CS)-H), amino (-NH 2),List-(C 1-C 24Alkyl) replace amino, two-(C 1-C 24Alkyl) replace amino, list-(C 5-C 24Aryl) replace amino, two-(C 5-C 24Aryl) replace amino, C 1-C 24Alkyl amido (-NH-(CO)-alkyl), C 6-C 24Acrylamido (-NH-(CO)-aryl), imino group (-CR=NH, wherein R=hydrogen, C 1-C 24Alkyl, C 5-C 24Aryl, C 6-C 24Alkaryl, C 6-C 24Aralkyl, etc.), C 2-C 20Alkyl imino (-CR=N (alkyl), wherein R=hydrogen, C 1-C 24Alkyl, C 5-C 24Aryl, C 6-C 24Alkaryl, C 6-C 24Aralkyl, etc.),Aryl imino group (-CR=N (aryl), wherein R=hydrogen, C 1-C 20Alkyl, C 5-C 24Aryl, C 6-C 24Alkaryl, C 6-C 24Aralkyl, etc.), nitro (-NO 2), nitroso (-NO), sulfo group (-SO 2OH), sulphonic acid ester (SO 2O-), C 1-C 24Alkyl alkylthio base (-S-alkyl; Be also referred to as " alkylthio "), C 5-C 24Sulfur alkyl aryl (-S-aryl; Be also referred to as " arylthio "), C 1-C 24Alkyl sulphinyl (-(SO)-alkyl), C 5-C 24Aryl sulfonyl kia (-(SO)-aryl), C 1-C 24Alkyl sulphonyl (-SO 2-alkyl), C 1-C 24Monoalkylaminosulfonyl-SO 2-N (H) alkyl), C 1-C 24Dialkyl amino sulfonyl-SO 2-N (alkyl) 2, C 5-C 24Aryl sulfonyl (-SO 2-aryl), boryl (-BH 2), borono (-B (OH) 2), borate (-B (OR) 2, wherein R is alkyl or other alkyl), phosphoryl (-P (O) (OH) 2), phosphonate radical (-P (O) (O) 2), phosphinic acids root (P (O) (O-)), dioxy phosphino (-PO 2) and phosphine (-PH 2); And hydrocarbyl portion C 1-C 24Alkyl (preferably C 1-C 12Alkyl, it is more preferable to be C 1-C 6Alkyl), C 2-C 24Thiazolinyl (preferably C 2-C 12Thiazolinyl, it is more preferable to be C 2-C 6Thiazolinyl), C 2-C 24Alkynyl (preferably C 2-C 12Alkynyl, it is more preferable to be C 2-C 6Alkynyl), C 5-C 24Aryl (preferably C 5-C 24Aryl), C 6-C 24Alkaryl (preferably C 6-C 16Alkaryl) and C 6-C 24Aralkyl (preferably C 6-C 16Aralkyl).In these substituent structures, " alkyl ", " alkylidene group ", " thiazolinyl ", " alkenylene ", " alkynyl ", " alkynylene ", " alkoxyl group ", " aromatics ", " aryl ", " aryloxy ", " alkaryl " and " aralkyl " part can be optionally that fluoridize or fluoridized.In addition, the alcohol mentioned, aldehyde, amine, carboxylic acid, ketone or other similar reactive functional groups also comprise their protected analogue.Such as, the hydroxyl mentioned or alcohol also comprise wherein hydroxyl by those substituting groups of following protection: ethanoyl (Ac), benzoyl (Bz), benzyl (Bn, Bnl), 'beta '-methoxy oxyethyl group methyl ether (MEM), dimethoxytrityl, [two-(4-p-methoxy-phenyl) phenyl methyl] (DMT), methoxymethyl ether (MOM), Methoxytrityl [(4-p-methoxy-phenyl) diphenyl methyl, MMT), p-methoxy-benzyl ether (PMB), methyl thio methyl ether, pivalyl (Piv), THP trtrahydropyranyl (THP), tetrahydrofuran (THF) (THF), trityl (trityl group, Tr), (the most frequently used silicon ether comprises trimethyl silyl (TMS) to silicon ether, t-butyldimethylsilyl (TBDMS), triisopropyl silyloxy methyl (TOM), with triisopropyl silyl (TIPS) ether), ethoxyethyl group ether (EE).The amine mentioned also comprise wherein amine by those substituting groups of following protection: BOC glycine, carbobenzoxy-(Cbz) (Cbz), p-methoxy-benzyl carbonyl (Moz or MeOZ), tertiary butyl oxycarbonyl (BOC), 9-fluorenylmethoxycarbonyl groups (FMOC), ethanoyl (Ac), benzoyl (Bz), benzyl (Bn), carbamate, p-methoxy-benzyl (PMB), 3,4-dimethoxy-benzyls (DMPM), p-p-methoxy-phenyl (PMP), tosyl group (Ts) group or sulphonamide (Nosyl and Nps) group.Mention containing the substituting group of carbonyl also comprise wherein carbonyl by the substituting group of following protection: acetal radical or ketal group, acylal base or Dai Senji (diathane group).The substituting group containing carboxylic acid or carboxylate group mentioned also comprise wherein carboxylic acid or carboxylate group by the substituting group of following protection: its methyl esters, benzyl ester, the tert-butyl ester, 2; the dibasic phenol of 6-(such as 2; 6-xylenol, 2; 6-diisopropyl phenol, 2,6 di t butyl phenol) ester, silyl ester, ortho ester Huo oxazoline.
At least one hydrogen atom meaning to combine in alkyl, alkyl, alkene, cycloolefin or other parts as carbon (or other) atom as " functionalized " in " functionalized alkyl ", " functionalized alkyl ", " functionalized alkene ", " functionalized cycloolefin " and analogue is such as here replaced with above-described those by one or more functional group.Term " functional group " means to comprise any functional substance being suitable for purposes described herein.Especially, as used herein, functional group must possess the ability to the corresponding functional group reactions in stromal surface or bonding.
In addition, if specific group allows, so above-mentioned functional group can by one or more other functional group or such as enumerated particularly above by one or more hydrocarbyl portion those replace further.Similarly, hydrocarbyl portion mentioned above such as can be enumerated particularly by one or more functional group or other hydrocarbyl portion those replace further.
The situation that " optional " or " optionally " means subsequent descriptions can or can not occur, the example that this description is comprised example that wherein this situation occurs and wherein this situation do not occur.Such as, phrase " optionally replaces " and means non-hydrogen substituent and can or can not be present on given atom, and therefore, this description comprises the structure that wherein there is non-hydrogen substituent and the structure that wherein there is not non-hydrogen substituent.
The present invention includes to for reducing the chemical system of C-O key, C-N key and the C-S key embodiment relevant with method.Specific embodiments provides for reducing the chemical system of C-O key, C-N key and C-S key, and every individual system comprises the mixture of (a) at least one organosilane and (b) at least one highly basic; Described system optionally comprise at least one molecular hydrogen donor compound, molecular hydrogen or the two, and described system preference ground be substantially without the compound of transition metal.Comprise can those transition metal of catalysis silicon alkyl reaction can be present in system described herein or method with the level that catalytic activity is associated usually therewith although some embodiment provides, the existing optional and be not desirable in many cases of this metalloid (as catalyzer or look on compound).Accordingly, in preferred embodiments, system and way is " substantially without transistion metal compound ".As used herein, term " substantially without transistion metal compound " intention reflects, this system is effective for the expection object of its reduction C-O key, C-N key and C-S key, even if do not exist any external source (that is, by add wittingly or otherwise to add) transition-metal catalyst time.Unless otherwise stated, otherwise so, term " substantially without transistion metal compound " is defined as and reflects, the aggregate level of the transition metal in reduction system is less than about 50ppm as being measured by ICP-MS of describing in embodiment 2 below independently or under the existence of organic substrate.The concentration that other embodiments additionally provide transition metal is less than about 100ppm, 50ppm, 30ppm, 25ppm, 20ppm, 15ppm, 10ppm or 5ppm extremely about 1ppm or 0ppm.As used herein, term " transition metal " is defined as and comprises Co, Rh, Ir, Fe, Ru, Os, Ni, Pd, Pt, Cu or its combination.In other concrete independently embodiment, the concentration as the Ni measured by ICP-MS is less than 25ppm, is less than 10ppm, is less than 5ppm or is less than 1ppm.
In addition, as used herein, term " reduction (as in C-O key, C-N key and C-S key) " or " reductive cleavage " refer to wherein O, N or S part by less electronegative group such as and comprise the chemical conversion that H, D or Si replace.
Although the exposure of this system to water and oxygen can be limited, in certain embodiments, chemical system and method are carried out in the environment of both anhydrous, oxygen substantially or water and oxygen.Unless otherwise specified, otherwise the level that term " anhydrous substantially " refers to water is less than about 500ppm and " substantially no oxygen " refers to the level of oxygen corresponding to the dividing potential drop being less than 1 holder.If statement, so other independently embodiment can provide: the level that " anhydrous substantially " refers to water is less than 1.5%, 1%, 0.5%, 1000ppm, 500ppm, 250ppm, 100ppm, 50ppm, 10ppm or 1ppm and " substantially no oxygen " refer to the oxygen level of dividing potential drop corresponding to being less than 50 holders, 10 holders, 5 holders, 1 holder, 500 millitorrs, 250 millitorrs, 100 millitorrs, 50 millitorrs or 10 millitorrs.
Although be not intended to the constraint (especially because it acts on still the unknown) of the exactness being subject to any proposed interaction mechanism, but show as that during reduction process, there is hydrogen for carrying out reductive cleavage be important, even if only proceed to hydrogen seem by the degree (vide infra) produced during reduction process, and the existence of hydrogen looks and improves reductive cleavage described herein (if not necessity) or the shortage of hydrogen detracts reductive cleavage described herein.Enjoyably, molecular hydrogen donor compound add also when reducing C-O key, C-N key and C-S key to system have favourable influence (see, such as, embodiment 5.9, table 2, project 18), and hydride does not have these favourable influence (such as apparently to body (comprising such as borohydride, alanate or tin hydride), see embodiment 5.12, table 4, project 3,5-7).Exemplary hydrogen donor compound can comprise such as following compound: 1，3-cyclohexadiene, 1，4-cyclohexadiene, 1,2-cyclohexadiene, 1,4-cyclohexadiene, 1,2-dihydronaphthalene, Isosorbide-5-Nitrae-dihydronaphthalene, 1,2-dihydroquinoline, 3,4-dihydroquinoline, 9,10-dihydroanthracenes or tetralin.
Mechanism (system and way is operated by this mechanism) is not yet understood, and contriver is not subject to about the exactness of any particular theory of the pattern of mechanism or the constraint of incorrect property, but some observation on indicating that activity reducing agent silicon matter can be the possibility of organosilicate.In addition, as described herein, although reductive cleavage is also often with the silylated existence of organic substrate, now this is unclear, no matter this type of material be whether intermediate, by product or the two.But this finds out really, the existence of hydrogen donor and hydrogen itself plays an important role when determining transforming degree and cracking and silylated relative quantity; See embodiment 5.9, table 2.
The importance of hydrogen or hydrogen donor can be found out by the result of the series of experiments of particular manipulation in the existence of hydrogen or hydrogen donor wherein.As described in the following Example 3, many experiments are carried out in the Glass Containers of sealing.The headspace analysis of the reaction mixture of these sealings indicates H 2formation.In order to determine its importance, and carry out other experiment, wherein make reaction open to the atmosphere of argon gas, so create the huge minimizing (embodiment 5.9 compensated by the silylanizing increased in the formation of reductive cleavage product, table 2, item compared 4-6).This result shows, dihydro may be important for preventing the decomposition of Active reducing substances.Regulating in optionally research further by closing free radical path, experiment uses 1，4-cyclohexadiene to carry out as nonpolar hydrogen donor cosolvent, and the exclusiveness causing having 2 of 95% yield forms (embodiment 5.9, table 2, project 18).These results show that the optionally ability regulating reaction by changing reaction conditions.
As used herein, term " organosilane " refers to the compound or reagent with at least one silicon-hydrogen (Si-H) key.Organosilane can also contain silicon-carbon bond, silicon-oxygen key, silicon-nitrogen key or its combination, and can be monomer or be comprised in oligopolymer framework or polymer frame, comprises and is linked to heterogeneous supporting structure or homogeneous supporting structure.In certain embodiments, these organosilanes can comprise the compound of at least one formula (I) or formula (II):
(R) 4-mSi(H) m(I) R—[—SiH(R)-O—] n—R(II)
Wherein: m is 1,2 or 3,1 is preferably;
N is from about 5 to about 500, from about 10 to about 100 or from the scope of about 25 to about 50; And
R is the C optionally replaced independently 1-12alkyl or assorted alkyl, C 5-20aryl or heteroaryl, C 6-30alkaryl or assorted alkaryl, C 6-30aralkyl or heteroaralkyl ,-O-C 1-12alkyl or assorted alkyl ,-O-C 5-20aryl or heteroaryl ,-O-C 6-30alkaryl or assorted alkaryl ,-O-C 6-30aralkyl or heteroaralkyl, and if be substituted, so substituting group can be phosphonate radical (phosphonato), phosphoryl, phosphinyl (phosphanyl), phosphino-, sulfonate radical (sulfonato), C 1-C 20alkyl alkylthio base, C 5-C 20sulfur alkyl aryl, C 1-C 20alkyl sulphonyl, C 5-C 20aryl sulfonyl, C 1-C 20alkyl sulphinyl, C 5-C 20aryl sulfonyl kia, sulfonamido, amino, amido, imino-, nitro, nitroso-group, hydroxyl, C 1-C 20alkoxyl group, C 5-C 20aryloxy, C 2-C 20alkoxy carbonyl, C 5-C 20aryloxycarbonyl, carboxyl, carboxylate radical (carboxylato), sulfydryl, formyl radical, C 1-C 20thioesters, cyano group, cyanate radical, thiocyanate radical, isocyanic ester, isothiocyanic acid ester, formamyl, epoxy group(ing), styryl, silyl, silyloxy, silylation, siloxanes azanyl (siloxazanyl), borate (boronato), boryl or halogen or metallic group or containing metalloid group; wherein metalloid is Sn or Ge, and wherein substituting group can optionally to comprising the insoluble of aluminum oxide, silicon-dioxide or carbon or sl. sol. supporting dielectric provides link (tether).Exemplary, nonrestrictive organosilane comprises (R) 3siH, wherein R is C 1-6alkyl, the arylalkyl silane such as PhMe of triethyl silicane and tributyl silane, mixing specifically 2siH, and polymer materials such as polymethyl hydrogen siloxane (PMHS).
As used herein, term " highly basic " refer to especially but not only hydrogen atom is had to the compound of strong affinity in non-aqueous media.In concrete independently embodiment, at least one highly basic comprises basic metal or basic metal hydride or alkoxide.Then it should be understood that this definition is not strictly limited to classical conjugate acid and base model because the conjugate acid of hydride will be dihydro.The measurement of this " strong affinity " can be that this highly basic (if reacting with water) will react with in fact from its complete form oxyhydroxide.Other " highly basic " can be regarded as comprising alkyl lithium compounds or acid amides ion, such as two (trimethyl silyl) potassium amide.
Seem that there is the Activity Rank relevant to the counter ion of highly basic, make the hydride and the alkoxide that preferably use caesium and potassium.The exemplary hydride that can be used in the present invention comprises hydrolith and potassium hydride KH.Similarly, can in embodiment 5.9, table 2, the impact of temperature on the validity of the reaction with hydride is seen in project 13 and 24, the diphenylene-oxide wherein carried out at 100 DEG C and the reaction of KH cause the low conversion rate of simple check hydrolysis products xenyl-2-alcohol and low formation level, and at 165 DEG C, carry out similar experiment create mainly to the substantially quantitative conversion of this product.
Useful alkoxide comprises and comprises C 1-12straight chain or the moieties of side chain or C 5-10those of aromatic fractions or heteroaromatic moiety, such as methylate, ethylate, propylate, butanolate, 2-ethyl-hexanol salt or phenylcarbinol salt.Each in these seem to give comparable reactivity (see, such as, embodiment 5.9, table 2, item compared 17,25-26 and 28).In addition, the selection of counter cation also affects the validity of the activity of chemical system, makes the alkoxide of potassium or caesium be preferred.More specifically, potassium methylate, potassium ethylate and potassium tert.-butoxide and 2-ethyl hexyl alcohol caesium have been shown in this is effective especially on.By comparing, Et 3the reaction of SiH and trimethyl carbinol lithium or sodium tert-butoxide do not provide diphenylene-oxide to biphenyl-2-alcohol conversion (see, such as, embodiment 5.9, table 2, project 29-31), show counter ion produce activity reducing agent material time and possibly at activated substrate ether time play a crucial role.Similarly, carry out result in the reaction of potassium tert.-butoxide under the existence of 18-hat-6 being enough to serve as potassium sequestrant and almost completely inhibit this reaction (table 4, embodiment 5.12, project 2).
Although it is particularly important that the relative quantity of organosilane and highly basic is not believed, as long as but the two is all present in an amount sufficient, in certain embodiments, organosilane and at least one highly basic just jointly exist with the mol ratio in from about 20:1 to the scope of about 1:2 relative to each other.In other embodiments, these ratios can be about 5:1 to about 1:2, from about 3:1 to about 1:3 or from about 3:2 to the order of magnitude of about 2:3.Going back in other embodiments, when organosilane is used as the solvent of reduction, it is effective that system has been shown as.In addition, the expection organic substrate for chemical reduction can be used as solvent.In certain embodiments, chemical system can be regarded as comprising containing aerobic, nitrogen, sulphur or its organic substrate combined, comprise the organic substrate be wherein comprised in biomass (such as, xylogen, sugar), biomass liquefying thing, biological pyrolysis oil, black liquor, coal, gelatin liquefaction thing, Sweet natural gas or oil batch processing thing or process flow.
Reduction system can also comprise the solvent except organosilane.As illustrated at present, preferred solvent seemingly aprotic solvent.In addition, although reductive cleavage reaction also seems to like higher temperature, be not necessarily limited to this constraint (such as ethyl hexyl alcohol caesium has demonstrated and reduced C-O key with triethyl silicane at ambient room temperature).Therefore, there is lower end by the restriction of the value of about 25 DEG C, 50 DEG C, 75 DEG C, 100 DEG C, 125 DEG C, 150 DEG C, 175 DEG C or 200 DEG C and upper end is seemingly preferred by the solvent of the boiling point (at one atm) in the scope of the value restriction of about 450 DEG C, 425 DEG C, 400 DEG C, 375 DEG C, 350 DEG C, 325 DEG C, 300 DEG C, 275 DEG C or 250 DEG C.So, exemplary, a nonrestrictive boiling spread is from about 80 DEG C to about 350 DEG C.Exemplary, nonrestrictive solvent comprises benzene,toluene,xylene, sym-trimethylbenzene, naphthalene, methylcyclohexane He diox.
As will be described further below, these chemical reduction systems can make C-O key, C-N key or C-S key reductive cleavage.In certain embodiments, these are alkyl C-O key, the C-O key of C-N key or C-S key or aromatics, C-N key or C-S key.In the context of the C-O key of alkyl or aromatics, C-N key or C-S key, term " alkyl " and " aromatics " refer to the character of the carbon that Sauerstoffatom, nitrogen-atoms or sulphur atom are bonded to.As used herein, general term " aromatics " refers to the loop section of the H ü ckel 4n+2 rule meeting aromaticity, and comprise aryl (namely, carbocyclic ring) both structure and heteroaryl moieties, these structures comprise aryl, aralkyl, alkaryl, heteroaryl, heteroaralkyl or alkane heteroaryl moieties.In addition, the C-O key of aromatics, C-N key or C-S key can be configured in member ring systems is inner ring (such as, pyridine, furans, pyrroles or thiophene) or is (such as, as methyl-phenoxide) outside ring for aromatic ring structure.
In this, the present invention can reduce C-O key, C-N key, C-S key or its combination chemical system in be described, but also should be apparent that, the present invention also comprise implement these transform methods.In other words, various other embodiments comprise wherein when be enough to reduce these keys at least partially make to comprise C-O key, C-N key, C-S key or the organic substrate of its combination and any those methods contacted of above-mentioned chemical system.In other words, some embodiment provides the method for the C-X key in reduction organic substrate, wherein X is O, N or S, described method comprises: be enough to reduce a certain amount of matrix C-X key at least partially condition under, make the matrix comprising at least one C-O key, C-N key or C-S key of described amount and comprise the chemical system of (a) at least one organosilane with the mixture of (b) at least one highly basic and contact; Wherein said chemical system preferably substantially without transistion metal compound, and described chemical system optionally comprise at least one molecular hydrogen donor compound, molecular hydrogen or the two.In this context, term " reduction " and " reductive cleavage " have and above-described identical definition; That is, at least certain part comprising wherein O, N or S part by less electronegative group such as and comprise the chemical conversion that H, D or Si replace.There is described herein the concrete essence of these chemical conversions.
In addition, in the context of method, term " substantially without transistion metal compound " has and the identical implication described for chemical system above and related embodiment; That is, reflect that the method is carried out effectively when existing without any transition-metal catalyst of having a mind to add.Unless otherwise stated, otherwise when described method or system, term definition is that the aggregate level of reflection transition metal is less than about 50ppm as being measured by ICP-MS of describing in embodiment 2 below.The concentration that other embodiments additionally provide transition metal is less than about 100ppm, 50ppm, 30ppm, 25ppm, 20ppm, 15ppm, 10ppm or 5ppm extremely about 1ppm or 0ppm.As used herein, term " transition metal " is defined as and means Co, Rh, Ir, Fe, Ru, Os, Ni, Pd, Pt, Cu or its combination.In other independently embodiment, the concentration as the Ni measured by ICP-MS is less than 25ppm, is less than 10ppm, is less than 5ppm or is less than 1ppm.Note at this, some embodiment of chemical system can comprise at least one organosilane and highly basic, and optionally comprise at least one molecule hydrogen donor, at least one matrix, extra solvent or its combination, will be appreciated that, when consider in the combination of these mixtures each time, the level that independently embodiment provides transition metal keeps below the level just described.
In the context of method, term " substantially anhydrous and/or oxygen " has and the identical implication described for system itself above and related embodiment.Similarly, identical organosilane, highly basic, solvent, ratio and the operational condition that are described as can be used for system are applicable to use the method for this system.In addition, as shown in the embodiment, system be shown as when by the C-X key in like this operation so that organosilane and matrix with exist from about 1:2 to the ratio of about 10:1 and C-X key wherein in highly basic and matrix to exist from about 1:2 to the scope of about 10:1 time be useful.In embodiment 5.9, the commentary of the result shown in table 2 provides the helpful indicator of the impact about the ratio in these limit values, and each ratio or its combination represent single embodiment of the present invention.
Method by carry out " be enough to reduce a certain amount of matrix C-X key at least partially condition under " in be described.This type of condition comprises and is heated to the organic substrate be touched and chemical system from the temperature in the scope of about 25 DEG C to about 450 DEG C.In independently embodiment, this heating can be carried out under at least one temperature in the scope from about 25 DEG C, about 50 DEG C, about 75 DEG C, about 100 DEG C, about 150 DEG C or about 200 DEG C to about 450 DEG C, about 400 DEG C, about 350 DEG C, about 300 DEG C, about 250 DEG C, about 200 DEG C or about 150 DEG C, comprises the temperature exemplified herein.Preferably but not necessarily, carry out in the solvent of this heating at the temperature of the boiling point lower than solvent, but and carry out in solvent preferably not necessarily at one atm at the temperature of the boiling point lower than solvent.
The cracking that term " to reduce the C-X key at least partially of matrix of described amount " refers to wherein single C-X key proceeds to the condition being less than quantitative yield, the cracking referring to wherein single C-X key proceeds to the condition of quantitative yield, refer to wherein multiple C-X key to be present in matrix (individuation compound or its mixture) and the condition that only the C-X key of a type is cleaved, or its combination.In order to the object of this description, unless otherwise stated, otherwise reaction conditions is thought fully, if at least 5% of at least one C-X key (wherein X=O, N or S) is cleaved by reaction.Higher yield is preferred, especially when processing individuation compound, so other independently embodiment provides reaction conditions be considered to sufficient, if at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90% or at least 95% of at least one C-X key is cleaved by reaction.In relevant embodiment, method can produce such product, at least one in this product in C-X key be reduced relative to the original amount be present in matrix compounds scope from about 10%, about 20%, about 30%, about 40%, about 50% or about 60% lower value to about 100%, about 95%, about 90%, about 80%, about 70%, about 60%, about 50% or about 40% the amount of higher limit.
This high yield of any single bonding can be optional, if matrix be such as xylogen (see, such as, Fig. 1), the extension array of interconnection aromatic substance that finds in coal or petroleum products, result can be measured by the minimizing of the molecular weight of initial substrate in this case.
Under nominally the same terms otherwise, method also makes different C-X bond cleavage solutions with different efficiency.Such as, as in embodiment 5.11, seeing in scheme 1 and 2, aliphaticly showing when being comprised in same matrix different with the C-O key of aromatics.In addition, C-O key and C-N key produce the product with residual alcohol or amine bonding substantially, and usually produce such product for the same reaction conditions of the matrix with C-S key, and S fully removes from this product.There is to be difficult to even in history the middle generation of matrix (the dibenzothiophene class of such as, being obstructed) of desulfurization in this desulfurization.
The method is seemingly exercisable about organic aromatics matrix, and wherein organic substrate comprises the combination of at least one C-O key, at least one C-N key, at least one C-S key or this type of C-O key, C-N key or C-S key.Although method has used multiple aromatics matrix or heteroaromatic matrix to verify, cleaved C-O key, C-N key or C-S key be the C-O key of aromatics, C-N key or C-S key not necessarily.In certain embodiments, at least one in C-O key, C-N key or C-S key comprises aromatics carbon.In this group, the C-O key of aromatics, C-N key or C-S key can be outside inner ring or ring for aromatic ring.Term " inner ring " and " outside ring " refer to O, N or the S-phase position for aromatic ring system.Such as, " inner ring " refers to wherein both carbon and corresponding Sauerstoffatom, nitrogen-atoms or sulphur atom and is all comprised in the key in aromatic ring; Furans, pyrroles and the thiophene C-O key respectively containing inner ring, C-N key and C-S key.Therefore, organic substrate can comprise and includes but not limited to the following heteroaryl moieties optionally replaced: furans, pyrroles, thiophene, cumarone, benzopyrrole, thionaphthene, 2,3-Dihydrobenzofuranes, xanthene, 2, the structure of 3-dihydrobenzo pyrroles, 2,3-dihydrobenzo thiophene, diphenylene-oxide, dibenzopyrrole, dibenzothiophene or the diphenylene-oxide be obstructed, dibenzopyrrole or dibenzothiophene.Term " structure of the diphenylene-oxide be obstructed, dibenzopyrrole or dibenzothiophene " refers to exists the aryl, alkyl or the alkoxy substituent that optionally replace in 2,6 of diphenylene-oxide, dibenzopyrrole or dibenzothiophene.2,6-dimethyl Dibenzothiophene is an important example of the dibenzothiophene be obstructed.
Under contrast, term " outside ring " refer to such key, in this key, both carbon is all comprised in aromatic ring system, but corresponding Sauerstoffatom, nitrogen-atoms or sulphur atom are not included in aromatic ring system, and (in the case of nitrogen) vice versa.Such as, phenol, aniline (aniline), 1-methyl isophthalic acid H-pyrroles and the thiophenol C-O key respectively containing the aromatics outside ring, C-N key and C-S key.Phenyl ether, aniline, diphenyl sulfide, naphthyl ether, naphthylamines or naphthalene polysulfide moiety that exemplary organic substrate includes but not limited to optionally to replace, N-alkyl pyrroles or N-aryl-pyrrolidine or its combination.
As mentioned above, the method is also exercisable about organic aromatics matrix, and wherein cleaved C-O key, C-N key or C-S key are aliphatic (alkyl) C-O key, C-N key or C-S key.Usually, but not necessarily, aliphatic (alkyl) C-O key, C-N key or C-S key be wherein heteroatoms also by the C-O key of aromatics, C-N key or C-S key connect those, methyl-phenoxide (Ph-O-CH 3) and 1-methyl isophthalic acid H-pyrroles be only two examples.Enjoyably, and for the reason understood by halves, aromatic fractions goes out to extend beyond it affect heteroatomic ortho position the impact of bond cleavage solution is also observed.Such as, in two examples:
Other embodiments provide these methods can be applied to organic substrate in batches or individually in flow or in the flow of the part as mixture.In fact, attractively especially be, if organic substrate is comprised in oil, coal, Sweet natural gas, biomass (such as, xylogen, sugar), biological pyrolysis oil, biomass liquefying thing or black liquor flow or in process flow in batches, if or this stream or process flow are in batches provided for the solvent of this reaction, so apply these methods.
Recognize, provide the system of the cracking of C-O key, C-N key, C-S key and reaction can also provide the silylanizing of aromatics matrix or even aromatic solvent.This latter's silylanizing feature be the name submitted on October 2nd, 2013 be called " Transition-Metal-Free C-H Silylation ofAromatic Compounds " be designated as the common submission of attorney docket CTEK-0133 (CIT-6650) and the theme of the U.S. Patent application of CO-PENDING, this patent is also incorporated to its entirety by reference for all objects.The mechanism that system and way is operated by it is not yet understood, and such as, no matter silylanizing is the intermediate steps of scission reaction or common property thing or by product, but its Relative Contribution really showing as each branch can be handled by reaction conditions.Such as, if other factors are similar or equal, so it shows as the cracking that higher temperature and longer reaction times are conducive to C-O key in silylation reactive, C-N key, C-S key.Similarly, the use (relative to organosilane) of the shortage of hydrogen and hydrogen donor molecule and the substoichiometric amount of highly basic seems to be conducive to silylation reactive and is unfavorable for C-X cracking.
Following embodiment list intention supplement but not replace or replace before description.
Embodiment 1. 1 kinds is for reducing the chemical system of C-O key, C-N key and C-S key, described system comprises the mixture of (a) at least one organosilane and (b) at least one highly basic, described system preference ground substantially without transistion metal compound, and described system optionally comprise at least one molecular hydrogen donor compound, molecular hydrogen or the two.
The system of embodiment 2. as described in embodiment 1, also comprise at least one molecular hydrogen donor compound, hydrogen or the two.
The system of embodiment 3. as described in embodiment 1 or 2, described system can make C-O key, C-N key or C-S key reductive cleavage.
The system of embodiment 4. according to any one of embodiment 1 to 3, described system can make the C-O key of aromatics, C-N key or C-S key reductive cleavage.
The system of embodiment 5. as described in embodiment 4, wherein said C-O key, C-N key or C-S key are outside ring for aromatic moieties.
The system of embodiment 6. as described in embodiment 4, wherein said C-O key, C-N key or C-S key are inner ring for aromatic moieties.
The system of embodiment 7. according to any one of embodiment 1 to 3, described system can make aliphatic C-O key, C-N key or C-S key reductive cleavage.
The system of embodiment 8. according to any one of embodiment 1 to 7, described system is both anhydrous, oxygen or water and oxygen substantially.
The system of embodiment 9. according to any one of embodiment 1 to 8, the wherein organosilane of at least one organosilane contained (I) or formula (II):
(R) 4-mSi(H) m(I)R—[—SiH(R)-O—] n—R(II)
Wherein: m is 1,2 or 3; N is 10 to 100; And R is the C optionally replaced independently 1-12alkyl or assorted alkyl, C 5-20aryl or heteroaryl, C 6-30alkaryl or assorted alkaryl, C 6-30aralkyl or heteroaralkyl ,-O-C 1-12alkyl or assorted alkyl ,-O-C 5-20aryl or heteroaryl ,-O-C 6-30alkaryl or assorted alkaryl ,-O-C 6-30aralkyl or heteroaralkyl, and if be substituted, so substituting group can be phosphonate radical, phosphoryl, phosphinyl, phosphino-, sulfonate radical, C 1-C 20alkyl alkylthio base, C 5-C 20sulfur alkyl aryl, C 1-C 20alkyl sulphonyl, C 5-C 20aryl sulfonyl, C 1-C 20alkyl sulphinyl, C 5-C 20aryl sulfonyl kia, sulfonamido, amino, amido, imino-, nitro, nitroso-group, hydroxyl, C 1-C 20alkoxyl group, C 5-C 20aryloxy, C 2-C 20alkoxy carbonyl, C 5-C 20aryloxycarbonyl, carboxyl, carboxylate radical, sulfydryl, formyl radical, C 1-C 20thioesters, cyano group, cyanate radical, thiocyanate radical, isocyanic ester, isothiocyanic acid ester, formamyl, epoxy group(ing), styryl, silyl, silyloxy, silylation, siloxanes azanyl, borate, boryl or halogen or metallic group or containing metalloid group; wherein said metalloid is Sn or Ge, and wherein said substituting group can optionally to comprising the insoluble of aluminum oxide, silicon-dioxide or carbon or sl. sol. supporting dielectric provides link.
The system of embodiment 10. as described in embodiment 9, wherein said organosilane is (R) 3siH, wherein R is C 1-6alkyl.
The system of embodiment 11. according to any one of embodiment 1 to 10, wherein said at least one highly basic comprises hydride or the alkoxide of basic metal or basic metal.
The system of embodiment 12. according to any one of embodiment 1 to 11, wherein said at least one highly basic comprises the hydride of basic metal or basic metal.
The system of embodiment 13. as described in embodiment 12, wherein said at least one highly basic comprises hydrolith or potassium hydride KH.
The system of embodiment 14. according to any one of embodiment 1 to 11, wherein said at least one highly basic comprises the alkoxide of basic metal or basic metal.
The system of embodiment 15. as described in embodiment 14, wherein said at least one alkoxide comprises C 1-12straight chain or the moieties of side chain or C 5-10the part of aromatics or heteroaromatic.
The system of embodiment 16. as described in embodiment 15, wherein said at least one alkoxide comprises methylate, ethylate, propylate, butanolate or 2-ethyl-hexanol salt.
The system of embodiment 17. according to any one of embodiment 11 to 16, the hydride of wherein said basic metal or basic metal or alkoxide base (alkoxide base) are the alkoxide of potassium or caesium.
The system of embodiment 18. according to any one of embodiment 1 to 17, wherein said organosilane is triethyl silicane and described highly basic is potassium tert.-butoxide.
The system of embodiment 19. according to any one of embodiment 1 to 18, wherein said organosilane and described at least one highly basic jointly exist with the mol ratio in from about 20:1 to the scope of about 1:2 relative to each other.
The system of embodiment 20. according to any one of embodiment 1 to 19, also includes organic compounds, and described compound is both solvent, matrix or solvent and matrix.
The system of embodiment 21. as described in embodiment 20, wherein said organic compound is organic solvent, and described organic solvent has at one atm from the boiling point in the scope of about 25 DEG C to about 450 DEG C.
The system of embodiment 22. as described in embodiment 20 or 21, wherein said organic compound is containing aerobic, nitrogen, sulphur or its organic substrate combined.
Embodiment 23. is as the system of embodiment 22, and wherein said organic substrate is comprised in biomass (such as xylogen, sugar), biomass liquefying thing, biological pyrolysis oil, black liquor, coal, gelatin liquefaction thing, Sweet natural gas or petroleum technology stream.
The system of embodiment 24. according to any one of embodiment 1 to 23, wherein said transistion metal compound exists with the 10ppm that is less than of the weight relative to total system.
The system of embodiment 25. according to any one of embodiment 1 to 24, wherein said hydrogen donor compound comprises 1,3-cyclohexadiene, 1，4-cyclohexadiene, 1,2-cyclohexadiene, 1,4-cyclohexadiene, 1,2-dihydronaphthalene, Isosorbide-5-Nitrae-dihydronaphthalene, 1,2-dihydroquinoline, 3,4-dihydroquinoline, 9,10-dihydroanthracenes or tetralin.
Embodiment 26. 1 kinds reduces the method for the C-X key in organic substrate, wherein X is O, N or S, described method comprises: be enough to reduce a certain amount of described matrix described C-X key at least partially condition under, make the described matrix comprising at least one C-O key, C-N key or C-S key of described amount and comprise the chemical system of (a) at least one organosilane with the mixture of (b) at least one highly basic and contact; Wherein said chemical system preferably substantially without transistion metal compound, and described chemical system optionally comprise at least one molecular hydrogen donor compound, molecular hydrogen or the two.
The method of embodiment 27. as described in embodiment 26, also comprise at least one molecular hydrogen donor compound, hydrogen or the two.
The method of embodiment 28. as described in embodiment 26 or 27, wherein said organic substrate comprises at least one C-O key, and optionally comprises both at least one C-N key, C-S key or C-N key and C-S key.
The method of embodiment 29. as described in embodiment 26 or 27, wherein said organic substrate comprises at least one C-N key, and optionally comprises both at least one C-O key, C-S key or C-O key and C-S key.
The method of embodiment 30. as described in embodiment 26 or 27, wherein said organic substrate comprises at least one C-S key, and optionally comprises both at least one C-O key, C-N key or C-O key and C-N key.
The method of embodiment 31. according to any one of embodiment 26 to 30, also comprise at least one molecular hydrogen donor compound, molecular hydrogen itself or the two.
The method of embodiment 32. according to any one of embodiment 26 to 31, at least one in wherein said C-O key, C-N key or C-S key is the C-O key of aromatics, C-N key or C-S key.
The method of embodiment 33. as described in embodiment 32, at least one in wherein said C-O key, C-N key or C-S key is outside ring for aromatic moieties.
The method of embodiment 34. according to any one of embodiment 33, at least one in wherein said C-O key, C-N key or C-S key is inner ring for aromatic moieties.
The method of embodiment 35. according to any one of embodiment 26 to 34, wherein said matrix comprises phenyl ether, aniline, diphenyl sulfide, naphthyl ether, naphthylamines or the naphthalene polysulfide moiety or its combination that optionally replace.
The method of embodiment 36. according to any one of embodiment 26 to 35, wherein said matrix comprises furans, pyrroles, thiophene, cumarone, benzopyrrole, thionaphthene, 2,3-Dihydrobenzofuranes, 2,3-dihydrobenzo pyrroles, 2,3-dihydrobenzo thiophene, diphenylene-oxide, xanthene, dibenzopyrrole, dibenzothiophene or the diphenylene-oxide be obstructed, dibenzopyrrole or dibenzothiophene part.
The method of embodiment 37. according to any one of embodiment 26 to 32, at least one in wherein said C-O key, C-N key or C-S key is aliphatic C-O key, C-N key or C-S key.
The method of embodiment 38. according to any one of embodiment 26 to 37, described method is both anhydrous, oxygen or water and oxygen substantially.
The method of embodiment 39. according to any one of embodiment 26 to 38, the wherein organosilane of at least one organosilane contained (I) or formula (II):
(R) 4-mSi(H) m(I) R—[—SiH(R)-O—] n—R(II)
Wherein m is 1,2 or 3; N is 10 to 100; And R is the C optionally replaced independently 1-12alkyl or assorted alkyl, C 5-20aryl or heteroaryl, C 6-30alkaryl or assorted alkaryl, C 6-30aralkyl or heteroaralkyl ,-O-C 1-12alkyl or assorted alkyl ,-O-C 5-20aryl or heteroaryl ,-O-C 6-30alkaryl or assorted alkaryl ,-O-C 6-30aralkyl or heteroaralkyl, and if be substituted, so substituting group can be phosphonate radical, phosphoryl, phosphinyl, phosphino-, sulfonate radical, C 1-C 20alkyl alkylthio base, C 5-C 20sulfur alkyl aryl, C 1-C 20alkyl sulphonyl, C 5-C 20aryl sulfonyl, C 1-C 20alkyl sulphinyl, C 5-C 20aryl sulfonyl kia, sulfonamido, amino, amido, imino-, nitro, nitroso-group, hydroxyl, C 1-C 20alkoxyl group, C 5-C 20aryloxy, C 2-C 20alkoxy carbonyl, C 5-C 20aryloxycarbonyl, carboxyl, carboxylate radical, sulfydryl, formyl radical, C 1-C 20thioesters, cyano group, cyanate radical, thiocyanate radical, isocyanic ester, isothiocyanic acid ester, formamyl, epoxy group(ing), styryl, silyl, silyloxy, silylation, siloxanes azanyl, borate, boryl or halogen or metallic group or containing metalloid group; wherein said metalloid is Sn or Ge, and wherein said substituting group can optionally to comprising the insoluble of aluminum oxide, silicon-dioxide or carbon or sl. sol. supporting dielectric provides link.
The method of embodiment 40. as described in embodiment 39, wherein said organosilane is (R) 3siH, wherein R is C 1-6alkyl.
The method of embodiment 41. according to any one of embodiment 26 to 40, wherein said at least one highly basic comprises hydride or the alkoxide of basic metal or basic metal.
The method of embodiment 42. according to any one of embodiment 26 to 41, wherein said at least one highly basic comprises the hydride of basic metal or basic metal.
The method of embodiment 43. as described in embodiment 42, wherein said at least one highly basic comprises hydrolith or potassium hydride KH.
The method of embodiment 44. according to any one of embodiment 26 to 43, wherein said at least one highly basic comprises the alkoxide of basic metal or basic metal.
The method of embodiment 45. as described in embodiment 44, wherein said at least one alkoxide comprises C 1-12straight chain or the moieties of side chain or C 5-10the part of aromatics or heteroaromatic.
The method of embodiment 46. as described in embodiment 45, wherein said at least one alkoxide comprises methylate, ethylate, propylate, butanolate or 2-ethyl-hexanol salt.
The method of embodiment 47. according to any one of embodiment 39 to 46, the hydride of wherein said basic metal or basic metal or alkoxide base are the alkoxide of potassium or caesium.
The method of embodiment 48. according to any one of embodiment 26 to 47, wherein said organosilane is triethyl silicane and described highly basic is potassium tert.-butoxide.
The method of embodiment 49. according to any one of embodiment 26 to 48, wherein said organosilane and described at least one highly basic jointly exist with the mol ratio in from about 20:1 to the scope of about 1:2 relative to each other.
The method of embodiment 50. according to any one of embodiment 26 to 49, the C-X key in wherein said organosilane and described matrix is to exist from about 1:2 to the ratio of about 10:1.
The method of embodiment 51. according to any one of embodiment 26 to 50, the C-X key in wherein said highly basic and described matrix is to exist from about 1:2 to the scope of about 10:1.
The method of embodiment 52. according to any one of embodiment 26 to 49, wherein said organosilane exists to be enough to the amount of serving as the solvent of described method.
The method of embodiment 53. according to any one of embodiment 26 to 51, also comprises organic solvent.
The method of embodiment 54. as described in embodiment 53, described organic solvent has at one atm from the boiling point in the scope of about 25 DEG C to about 450 DEG C.
The method of embodiment 55. according to any one of embodiment 26 to 54, described method comprises and is heated to described organic substrate and described chemical system from the temperature in the scope of about 25 DEG C to about 450 DEG C.
The method of embodiment 56. according to any one of embodiment 26 to 55, wherein said transistion metal compound exists with the 10ppm that is less than of the weight relative to total system.
The method of embodiment 57. according to any one of embodiment 26 to 56, wherein said hydrogen donor compound comprises 1,3-cyclohexadiene, 1，4-cyclohexadiene, 1,2-cyclohexadiene, 1,4-cyclohexadiene, 1,2-dihydronaphthalene, Isosorbide-5-Nitrae-dihydronaphthalene, 1,2-dihydroquinoline, 3,4-dihydroquinoline, 9,10-dihydroanthracenes or tetralin.
The method of embodiment 58. according to any one of embodiment 26 to 57, wherein said organic substrate is comprised in biomass (such as xylogen, sugar), biomass liquefying thing, biological pyrolysis oil, black liquor, coal, gelatin liquefaction thing, Sweet natural gas or petroleum technology stream.
The method of embodiment 59. according to any one of embodiment 26 to 58, wherein said method is carried out in biomass (such as xylogen, sugar), biomass liquefying thing, biological pyrolysis oil, black liquor, coal, gelatin liquefaction thing, Sweet natural gas or petroleum technology stream.
The method of embodiment 60. according to any one of embodiment 26 to 59, wherein said method produces such product, in the product in described C-X key at least one with scope from relative to the amount be primitively present in described matrix compounds about 40% to 100% amount be reduced.
Embodiment
Some in the concept providing following examples to describe in present disclosure with illustration.Although each embodiment is considered to the concrete independent embodiment providing composition, preparation method and purposes, none embodiment should be considered to limit more general embodiment described herein.
In the examples below, although made an effort to guarantee the accuracy about used numeral (such as amount, temperature etc.), some experimental error and deviation should be taken into account.Unless otherwise directed, otherwise temperature is with degree Celsius, pressure or close to normal atmosphere.
Embodiment 1: general information
Unless otherwise specified, otherwise all reactions all use standard Shu Lunke line technology to implement in a nitrogen atmosphere under an argon atmosphere or in vacuum atmosphere glove box in dry glass vessel.Sym-trimethylbenzene (purity >=99.0% (GC)) comes degassed by three freezing-pump-thaw cycles before the use.Other all solvents are by carrying out purifying and degassed further with argon gas through solvent purification post.(1) for the NMR solvent CaH of air-sensitive experiment 2dry and by vacuum transfer or be distilled in dry Shu Lunke bottle, and use argon-degassed subsequently.Triethyl silicane (99%) and deuterated triethyl silicane (97 atom %D) purchased from Sigma-Aldrich and before the use come degassed by three freezing-pump-thaw cycles, and the liquid reagent of other commercially available acquisitions is similarly processed.Two-4-(methyl) phenyl ether, 1-naphthols, beta naphthal, 4-tert.-butylbenzene methyl ether, 4-methylanisole, 1,3-bis-phenoxy group benzene, 2-methoxynaphthalene and 1.0M tetrabutyl ammonium fluoride THF solution are purchased from Sigma-Aldrich and in statu quo use.Distillation level KO-t-Bu (99.99%) experiences vacuum-sublimation (30 millitorrs, 160 DEG C) before the use purchased from Sigma-Aldrich.4-(methoxyl group) diphenylene-oxide (2), two-4-(tertiary butyl) phenyl ether (3), naphthyl ether (3), 4-(phenyl) phenyl ether (3), 2-oxyethyl group naphthalene (4), 2-neopentyl oxygen naphthalene (4), 2-tert.-butoxy naphthalene (5) synthesize according to literature procedure.Standard NMR spectrum experiment carries out with following: Varian Mercury ( 1h, 300MHz) spectrograph, Varian Inova 400MHz spectrograph, be equipped with the Varian 500MHz spectrograph of AutoX probe or be equipped with the Varian600MHz spectrograph of Triax probe.Chemical shift is by using residual solvent peak as interior mark according to distance Me 4the ppm downfield of Si is reported.Spectrum uses the 7th edition MestReNova to carry out treatment and analysis.GC-FID analyzes and is being equipped with the upper acquisition of the Agilent 6890N gas chromatograph (Agilent) of HP-5 (5%-phenyl)-methyl polysiloxane capillary column.GC-MS analyzes and is being equipped with the upper acquisition of Agilent 6850 gas chromatograph (Agilent) of HP-5 (5%-phenyl)-methyl polysiloxane capillary column.High resolution mass spec (EI and FAB) is obtained by the mass spectroscopy device of Caltech.EPR spectrum is record on Bruker EMS spectrograph.
Embodiment 2:ICP-MS analyzes
ICP-MS analyzes and uses the 100mg sample of the MS equipment diphenylene-oxide of Caltech, triethyl silicane, sym-trimethylbenzene and potassium tert.-butoxide to carry out, this sample is added in 50mLDigiTUBE boiling pipe (SCP Science), next the Plasma Pure nitric acid (SCP Science) of 3.0mL is added into each boiling pipe, and be heated to 75 DEG C continue 36 hours.After cooking, to use Nanopure/Milli Q water that each diluted sample is carried out sample analysis to 50mL on HP 4500ICPMS spectrograph.Semi-quantitative analysis uses the 10ppm solution of the lithium of calibration, yttrium, cerium and thallium to carry out.Analyzed twice and give average measurements of each sample.(table 1).
Embodiment 3: general procedure
In glove box, 4mL screw cap vial is made to be mounted with corresponding matrix (0.1mmol, 1 equivalent), alkali (0.5-5 equivalent) and magnetic stirring bar, next solvent (1mL) and triethyl silicane (1-5 equivalent) are added in injection.React the screw cap closures of bottle teflon liner and heat under given temperature and time in glove box inside.After cooling to room-temperature, garnet is diluted to the reaction mixture diethyl ether (3mL) of black and carrys out quencher with the HCl that the 1N of 1ml is moisture carefully.Add tridecane (in GC mark), isolate organic layer and with ether (3mL) aqueous layer extracted until TLC contrast show be present in extract without UV active compound.Make the organic layer of merging through too short Celite pad and experience GC/FID, GC/MS and 1h-NMR analyzes.Unless otherwise directed, otherwise in preparation experiment, only have the product of the total recovery more than 2% separated and characterize.When naphthylalkyl ether, use different handling procedures (workup procedure).After cooling, reaction methylene dichloride (5mL) dilutes and carrys out quencher with the HCl that the 1N of 2mL is moisture carefully.Add tridecane, and mixture is transferred to separating funnel.Isolate organic phase, and by methylene dichloride (3mL) aqueous layer extracted.The organic layer merged is through anhydrous MgSO 4dry and filter.For all reactions, product uses GC/MS and GC/FID and NMR to identify by comparing with authentic sample.The soluble by-products of the trace observed in the reduction of naphthylalkyl ether comprises naphthalene, 1,2,3,4-naphthane and 5,6,7,8-tetralol.
Embodiment 4: the Synthesis and characterization of selected compound
Embodiment 4.1:4-(triethylsilyl) diphenylene-oxide (3)
Title compound is by the scheme for the synthesis of 4-(trimethyl silyl) diphenylene-oxide by Kelly and co-worker; The people J.Org.Chem. such as Bekele, H, prepared by the similar scheme of 1997,62,2259.(3) data: colourless oil. 1h-NMR (500MHz, CDC1 3): δ 7.99-7.96 (m, 2H ar), 7.59 (dual crest, J=10Hz, 1H ar), 7.54 (dd, J=2,5Hz, 1H ar), 7.48-7.44 (m, 1H ar), 7.37-7.33 (m, 2H ar), 1.03 (m, 15H, 3CH 2cH 3). 13C-NMR(126MHz,CDC1 3)δ161.30,156.05,133.57,126.92,122.52,122.48,121.58,120.68,111.75,7.63,3.59。HRMS:[C 18h 22oSi] calculated value 282.1440; Observed value 282.1444.
Two (triethylsilyl) diphenylene-oxide (4) of embodiment 4.2:4,6-
At-78 DEG C under argon gas, by tert-butyl lithium (the 1.7M solution in pentane of 17.5mL, 29.8mmol, 2.5 equivalents) add diphenylene-oxide (2.00g lentamente, 11.9mmol, 1 equivalent) and Tetramethyl Ethylene Diamine (11.1mL, 29.7mmol, the 2.5 equivalents) solution in tetrahydrofuran (THF) (50ml).Allow mixture to reach envrionment temperature and before interpolation chlorine triethyl silicane (10.1mL, 60mmol, 5 equivalents), make stirring continue to continue 4h.The mixture obtained stirs lasting other 16h at ambient temperature.After making reaction quencher with saturated ammonium chloride solution (40mL) and extract with diethyl ether (3 × 30mL), the organic layer of merging, through anhydrous sodium sulfate drying, filters and filtrate is concentrated in a vacuum.Crude reaction mixture carrys out purifying by silica gel chromatography (hexane), and make obtained product from the mixture recrystallization of methyl alcohol and Virahol (1:1) to obtain 4, two (triethylsilyl) diphenylene-oxide (1.28g of 6-, 2.45mmol, 28%), be colorless needles.(4) data: colorless needles.Fusing point=59-61 DEG C. 1H-NMR(300MHz,CDCl 3)δ7.97(dd,J＝3,9Hz,2H ar),7.54(dd,J＝3,9Hz,2H ar),7.33(t,J＝9Hz,2H ar),1.07-0.95(m,30H,6CH 2CH 3)。 13C-NMR(126MHz,CDC1 3)δ160.90,133.48,122.87,122.34,121.57,120.03,7.66,3.52。HRMS:[C 24h 36oSi 2] calculated value 396.2305; Observed value 396.2321.
Embodiment 4.3:3-(triethylsilyl) xenyl-2-alcohol (5)
Title compound is prepared (seeing below) by the cracking of 3.(5) data: white solid.Fusing point=44-46 DEG C 1h-NMR (300MHz, CDC1 3) δ 7.52-7.40 (m, 5H ar), 7.36 (dd, J=3,9Hz, 1H ar), 7.23 (dd, J=3,6Hz, 1H ar), 6.98 (t, J=9Hz, 1H ar), 5.41 (s, 1H, OH), 1.02-0.96 (m, 9H, CH 3), 0.91-0.83 (m, 6H, CH 2). 13C-NMR(75MHz,CDC1 3)δ157.25,137.51,135.97,131.30,129.58,129.39,128.01,127.17,123.04,120.40,7.79,3.69。HRMS:[C 18h 24oSi] calculated value 284.1596; Observed value 284.1583.
Embodiment 4.4:(3'-triethylsilyl) xenyl-2-alcohol (6)
Title compound is prepared (seeing below) by the cracking of 3.(6) data: colourless oil. 1H-NMR(500MHz,CDC1 3):δ7.57-7.56(m,1H ar),7.54-7.52(m,1H ar),7.49-7.44(m,2H ar),7.28-7.24(m,2H ar),7.02-6.99(m,2H ar),5.24(s,1H,OH),0.98(t,J＝10Hz,9H,CH 3),0.82(q,J＝15Hz,6H,CH 2)。 13C NMR(126MHz,CDC1 3):δ153.44,139.07,136.12,134.71,133.76,130.23,129.36,129.08,128.53,128.44,120.80,115.72,7.43,3.31。HRMS:[C 18h 24oSi] calculated value 284.1596; Observed value 284.1585.
Two (triethylsilyl) xenyl-2-alcohol (7) of embodiment 4.5:3,3'-
Title compound passes through at 100 DEG C, make diphenylene-oxide (1,840mg, 5.0mmol, 1 equivalent) and KOt-Bu (1.12g, 10mmol, 2 equivalents) and Et according to general procedure 3siH (4.0ml, 25mmol, 5 equivalents) is prepared for heating and continuous 20 hours in the toluene of 20ml.After acidic aqueous solution process, crude reaction mixture carrys out purifying to obtain 7 of 20mg (0.05mmol, 1%) together with other separated product by using hexane and the silica gel chromatography of hexane-ether (10:1).(7) data: oily solid 1h-NMR (300MHz, CDCl 3): δ 7.53-7.44 (m, 2H ar), 7.46-7.44 (m, 2H ar), 7.36 (dd, J=1.5,7.5Hz, 1H ar), 7.23 (dd, J=1.5,7.5Hz, 1H ar), 6.98 (t, J=7Hz, 1H ar), 5.42 (s, 1H, OH), 1.01-0.96 (m, 18H, 6CH 3) 0.91-0.77 (m, 15H, 6CH 2). 13C NMR(75MHz,CDCl 3):δ157.37,139.45,136.61,135.87,135.09,133.86,131.38,129.57,128.71,127.55,122.97,120.36,7.80,7.57,3.69,3.46。HRMS:[C 24h 38oSi 2] calculated value 398.2461; Observed value 396.2470.
Embodiment 5: selected reaction
Embodiment 5.1: the preparation scale cracking of diphenylene-oxide and deuterate experiment.
React according to general procedure by making diphenylene-oxide (1,250mg, 1.49mmol, 1 equivalent), KOt-Bu (500mg, 4.46mmol, 3 equivalents) and Et at 165 DEG C 3siH (713 microlitres, 4.46mmol, 3 equivalents) carries out for heating and continuous 20 hours in the sym-trimethylbenzene of 4.4mL.After with diethyl ether (5mL) dilution, first organic phase is used water (1mL) to wash and is next washed with 2.5NKOH solution (3 × 20mL).Collect alkalescence containing water section and by using CH 2cl 2(25ml) washing is once to remove any unexpected organism.Then, the alkalescence obtained containing water section with dense HCl acidifying until the pH of 1 and next use CH subsequently 2cl 2(3 × 25mL) extracts.Collect organic moiety and under reduced pressure concentrate to obtain pale yellow crystals.Obtaining xenyl-2-alcohol (2,198mg, 1.16mmol, 79%) by the purifying (gradient elution: 0% to 5% ethyl acetate) of the silica gel chromatography by hexane/ethyl acetate, is colorless solid.1 1h NMR spectrum and 13c NMR spectrum is specified consistent with those of authentic sample.
Be applied to the reductive cleavage of diphenylene-oxide but use Et now 3the same program of SiD obtains the xenyl-2-alcohol of non-deuterate, and separation yield is 76%.HRMS:[C 12h 10o] calculated value 170.0732; Observed value 170.0720.
Use Et 3siH and sym-trimethylbenzene-d 12repeat the xenyl-2-alcohol that experiment mentioned above obtains deuterate, separation yield is 73%.HRMS:[C 12h 4d 6o] calculated value 176.1108; Observed value 176.1115; FWHM ~ 4Da.Be applied to the reductive cleavage of diphenylene-oxide but use Et now 3siD and sym-trimethylbenzene d 12same program obtain the xenyl-2-alcohol of deuterate, separation yield is 79%.HRMS:[C 12h 4d 6o] calculated value 176.1108; Observed value 176.1108; FWHM ~ 4Da.
When making diphenylene-oxide and Et at 165 DEG C 3when SiD reacts in sym-trimethylbenzene, there occurs considerably less deuterium and be incorporated in 2.Consistent with this, at sym-trimethylbenzene-d 12in from Et 3siH or Et 3identical base peak in the high resolution mass spec spectrum of xenyl-2-alcohol prepared by SiD indicates, and there occurs under the reaction conditions and exchanges with the H/D fast of solvent.Enjoyably, as deuterate 2 proton, carbon and HSQC spectrum show, although the H/D all experiencing part of proton exchanges, only for adjacent OH position, this process reaches complete.
The cracking of embodiment 5.2:4-(triethylsilyl) diphenylene-oxide
React according to general procedure by making 4-Et at 100 DEG C 3si-diphenylene-oxide (3,141mg, 0.5mmol, 1 equivalent), KOt-Bu (112mg, 1mmol, 2 equivalents) and Et 3siH (401 microlitres, 2.5mmol, 5 equivalents) carries out for heating and continuous 20 hours in the toluene of 2ml.After acidic aqueous solution process, crude reaction mixture carrys out purifying to be separated 2-phenylphenol (2 by using hexane with the silica gel chromatography of hexane-ether (10:1), 30mg, 0.177mmol, 35%), 2-triethylsilyl-6-phenylphenol (5,37mg, 0.134mmol, 26%), 2-(3-triethylsilylphenyl) phenol (6,17mg, 0.063mmol, 12%).Do not consume 3 and the amount of product 1,4 and 7 use the chromatography of corresponding mixing portion after GC-FID analyze and obtain.
Embodiment 5.3: silylated diphenylene-oxide is as the research of the intermediate for C-O bond cleavage solution: attempt with the cracking of KOt-Bu
At 100 DEG C, in J.Young pipe, make parent material 3 (14.1mg, 0.05mmol, 1 equivalent) and KOt-Bu (being respectively 5.6mg or 11.2mg, 1 or 2 equivalents) under a nitrogen in the tritiate toluene of 0.8ml heating and continuous 20 hours.Pass through 1h NMR monitor reaction progress demonstrate in both cases without 3 conversion.Similarly, at 160 DEG C, make parent material 3 (28.2mg, 0.1mmol, 1 equivalent) or 4 (39.6mg 0.1mmol, 1 equivalents) and KOt-Bu (36.6mg) in the sym-trimethylbenzene of 0.3mL heating and continuous 20 hours.Crude reaction mixture by GC-FID or 1the subsequent analysis of HNMR discloses at 3% transformation efficiency of situation down to 1 of 3 and 5% transformation efficiency from 4 to 3.
The cracking of two (triethylsilyl) diphenylene-oxide of embodiment 5.4:4,6-
React according to general procedure by making 2-(3'-triethylsilylphenyl) phenol (4,39.6mg, 0.1mmol, 1 equivalent), KOt-Bu (33.6mg, 0.3mmol, 3 equivalents) and Et at 160 DEG C 3siH (48 microlitres, 0.3mmol, 3 equivalents) carries out for heating and continuous 20 hours in the sym-trimethylbenzene of 0.2ml.After acidic aqueous solution process, add interior mark and analyze crude reaction mixture by GC-FID.
The cracking of embodiment 5.5:4-(methoxyl group) diphenylene-oxide
React according to general procedure by making 4-MeO-diphenylene-oxide (8,89mg, 0.5mmol, 1 equivalent), KOt-Bu (112mg, 1mmol, 2 equivalents) and Et at 100 DEG C 3siH (401 microlitres, 2.5mmol, 5 equivalents) carries out for heating and continuous 20 hours in the toluene of 2ml.After aqueous solution process, crude reaction mixture carrys out purifying to reclaim the parent material 8 (3mg, the 0.015mmol that do not consume by using the silica gel chromatography of hexane and hexane-ether, 3%) and be separated diphenylene-oxide (1,8.4mg, 0.05mmol, 10%; Because the part of 1 contains a small amount of parent material 8, so quantitatively pass through 1h-NMR uses CH 2br 2carry out as interior mark), 1,1'-xenyl-2-alcohol (2,4.3mg, 0.025mmol, 5%), 4-Et 3si-diphenylene-oxide (3,11mg, 0.039mmol, 8%), 2-methoxyl group-6-phenyl-phenol (9, mg, 0.025mmol, 5%), 2-(3'-p-methoxy-phenyl) phenol (10,47mg, 0.235mmol, 47%).Attention: the compound only characterizing the yield had more than 2%.9 and 10 1h and 13c NMR spectrum is specified consistent with reported literature.
The synthesis of embodiment 5.6:4,6-bis-(methyl) diphenylene-oxide
Subzero 78 DEG C under argon gas, by tert-butyl lithium (the 1.7M solution in pentane of 17.5mL, 29.8mmol, 2.5 equivalents) add diphenylene-oxide (2.00g lentamente, 11.9mmol, 1 equivalent) and the solution of Tetramethyl Ethylene Diamine (11.1mL, 29.7mmol, 2.5 equivalents) in diethyl ether (50ml) in.Allow mixture to reach envrionment temperature and before interpolation methyl iodide (3.7mL, 60mmol, 5 equivalents), make stirring continue to continue 4h.The mixture obtained stirs lasting other 16h at ambient temperature.After making reactant quencher with saturated ammonium chloride solution (40mL) and extract with diethyl ether (3 × 30mL), the organic layer of merging, through anhydrous sodium sulfate drying, filters and filtrate is concentrated in a vacuum.Crude reaction mixture carrys out purifying by silica gel chromatography (hexane), and makes obtained product from recrystallizing methanol to obtain 4,6-dimethyl diphenylene-oxide (480mg, 2.45mmol, 21%), is colorless solid.(15) data: 1h-NMR (300MHz, CDC1 3): δ 7.75 (dd, J=1.0,6.0Hz, 2H ar), 7.24-7.20 (m, 4H ar), 2.61 (s, 6H, 2CH 3). 13c NMR (75MHz, CDC1 3): δ 155.07,128.00,124.17,122.60,122.02,118.2,15.41, HRMS:[C 14h 12o] calculated value 196.0888; Observed value 196.0884.
The cracking of embodiment 5.7:4,6-bis-(methyl) diphenylene-oxide
React according to general procedure by making 4,6-bis-(methyl) diphenylene-oxide (15,98mg, 0.5mmol, 1 equivalent), KOt-Bu (112mg, 1mmol, 2 equivalents) and Et at 100 DEG C 3siH (401 microlitres, 2.5mmol, 5 equivalents) heats and carries out for 20 hours in the toluene of 2ml.After aqueous solution process, crude reaction mixture carrys out purifying to obtain the product 16 of 77mg by using the silica gel chromatography of hexane-ether 4:1, is the oil of yellow.(16) data: 1h-NMR (500MHz, CDC1 3): δ 7.35 (t, J=7.5Hz, 1H ar), 7.25-7.22 (m, 2H ar), 7.20-7.18 (m, 1H ar), 7.11 (dual crest, J=10Hz, 1H ar), 7.05 (dual crest, J=7.5Hz, 1H ar), 6.87 (t, J=7.5Hz 1H ar), 5.31 (s, 1H, OH), 2.39 (s, 3H, CH 3), 2.30 (s, 3H, CH 3). 13C-NMR(126MHz,CDC1 3):δ150.68,139.26,137.36,130.51,129.93,129.39,128.73,127.83,127.76,126.20,124.70,120.25,21.60,16.33。HRMS:[C 14h 14o] calculated value 198.1045, observed value 198.1046.
At 165 DEG C, in sym-trimethylbenzene, repeat 100% transformation efficiency that this Therapy lasted causes parent material 15 for 20 hours, 96% yield of 16.
Although comprehensive study mechanism was still required before potential reaction path can be established reliably, but observe in the basic conditions without the conversion of 3 (4-(triethylsilyl) diphenylene-oxide) and without 4,6-dimethyl diphenylene-oxide 15 successfully reductive cleavage becomes corresponding xenyl-2-alcohol 16, because perhaps show the existence of the silylated aryl oxide in ortho position at first, so the intersexes of benzyne is seemingly impossible.
Embodiment 5.8:EPR tests
At 100 DEG C, inner at glove box, make diphenylene-oxide (1,16.8mg, 0.1mmol, 1 equivalent), KOt-Bu (22.5mg, 0.2mmol, 2 equivalents) and Et 3siH (80 microlitres, 0.5mmol, 5 equivalents) heats 1 hour in the toluene of 0.4ml.After such time, reaction mixture 0.8ml dilution with toluene and be filtered in EPR pipe.That reaction mixture is found to be EPR activity and spectra re-recorded (Fig. 2) in 20min after filtration.Recorded without in the control experiment of diphenylene-oxide, even if having lower intensity, but also been observed identical signal.These results are consistent with the reactive free radical that the aromatics substitution reaction for homolysis is recorded.1,10-phenanthroline together with KOt-Bu add be found to be harmful because do not observe the conversion of 1.
Embodiment 5.9: diphenylene-oxide split majorization of solutions details
Unless otherwise directed, otherwise experiment uses the general method described in embodiment 1 and 3 to carry out.Yield is reproducible in ± 2%.
Embodiment 5.10: the reductive cleavage of diaryl ether
In order to study the cracking of the aryl ethers C-O key in unstrained matrix (unstrained substrate) and probe, if this cracking is carried out when the undesirably over reduction of the aromatic moiety do not obtained, so diphenyl ether experiences the reaction conditions of above-mentioned non-additive optimization.This matrix provides benzene and phenol (table 3, project 1) with moderate yield, and remaining mass balance is mainly owing to silylated product and other unidentified products.Use this result grasped, assess the reactivity of more complicated diaryl ether.Symmetrical diaryl ether and asymmetric both diaryl ethers are all illustrated and are competent matrix and experience C-O cracking (project 2-7) with good extremely excellent efficiency.As compared with diphenyl ether, many in evaluated diaryl ether prove more reactive and allow to use relatively mild reaction conditions.When 1-naphthylphenyl ether (project 5), bond cleavage solution occurs to provide naphthalene and phenol with the yield respectively with 70% and 91% at naphthyl C-O key place regiospecificity, 1-naphthols or benzene do not detected.Use asymmetric dinaphthyl ether (project 5), C-O key reduced zone optionally occurs, thus provides beta naphthal and 1-naphthols respectively with good combination yield, and the ratio of two kinds of isomer is about 4:1.The asymmetric diphenyl ether (project 7) that phenyl is replaced with good total recovery and with for be rich in slightly more electron rich C-O key reduction medium regioselectivity and react, the instruction obvious impact of electronic effect in the site selectivity of C-O bond cleavage solution.This factor is conclusive for the selectivity of the cracking of 4-O-5 xylogen model, this 4-O-5 xylogen model contain be adjacent to destroyed C-O key strong methoxyl group to body (seeing below, scheme 2).This selectivity is complementary with the selectivity to be reported for the homogeneous Ni catalytic reduction with dihydro by other people, and wherein asymmetric diaryl ether is preferentially in the sidepiece place cracking of the more aromatic ring of electron deficiency.
Embodiment 5.11: the reductive cleavage of aryl alkyl ethers
The reduction of aryl alkyl ethers is carried out detecting the cracking selectivity of sp2 relative to sp3 C-O key under the optimal conditions being applied to diaryl ether.The reaction of 2-methoxynaphthalene obtains beta naphthal as primary product (scheme 1) using moderate yield.The GC-MS of crude reaction mixture analyzes to indicate exists micro-naphthalene together with 2-methylnaphthalene and the other material be reduced, and comprises the product of partially aromatic reduction.Also detect general derived from the silylated compound of beta naphthal.Similarly, the cracking under the same conditions of 2-oxyethyl group naphthalene obtains with the beta naphthal of slightly higher yield, but has same or similar by product.Spatially larger ether is studied with the variability of detecting C-O bond cleavage solution and possibility mechanism.Although large alkyl substituent is adjacent to ether oxygen, the reaction of 2-neopentyl oxygen naphthalene is to provide beta naphthal with using the not huger approximately uniform yield of matrix.Even 2-tert.-butoxy naphthalene is cleaved to obtain the naphthols of expecting, yield is 55% (scheme 1).That carries out at identical conditions does not still use the control experiment of triethyl silicane to provide beta naphthal when 2-oxyethyl group naphthalene and 2-tert.-butoxy naphthalene, although have the yield reduced substantially.Because 2-methoxyl group-matrix and 2-neopentyl oxygen-matrix this without the cracking of silane in keep complete, so eliminating mechanism may be operability.When attempting reducing 4-tert.-butylbenzene methyl ether and 4-methylanisole at the standard conditions, the yield of corresponding phenol is high, may be because the phenyl ring that is substituted has more challenging silylanizing (scheme 2) due to steric reasons.
Generally, the selectivity cut off for alkyl C-O key is formed with the selectivity wherein occurring observing in the C-O scission reaction of Ni that aryl C-O reduces and borine catalysis and contrasts.Also noteworthy is that, only observe the naphthalene nucleus hydrogenated products of trace under these conditions, the result of the ionic hydrogenation based on silane reported in this and document is formed and contrasts.
Have directiveness, make the diaryl ether 8 of methoxy substitution with 11 cracking (scheme 2) compared with the result presented above.Although aryl alkyl ethers shows strong preference for the alkyl oxygen on reduction aryl oxide key, both the methoxyl group matrix in scheme 2 all shows the reverse of regioselectivity, almost provides aryl oxide key breakdown products exclusively.Although be not intended to the constraint of the exactness by this theory, this effect can owing to the existence of giving body Sauerstoffatom at the C-O key ortho position of breaking in experience.Support that this deduction is the highly selective of the reductive ring open of the dibenzofuran derivative 8 mainly producing 10.Similarly, being preferably formed to be observed to phenol 12 and 13, there is similar selectivity in the cracking of xylogen model 11 of phenol and methyl-phenoxide.People can infer, and not by the constraint of the exactness of this theory, this effect can be rationalized by the Sauerstoffatom resonance stabilization of the positive charge gathered between the electrophilic pot-life of just destroyed C-O key.In order to test this hypothesis, making compound 3 experience this reaction conditions and being separated the phenol 5 and 6 of open loop and desilyated product 1 and 2 (scheme 2, illustration C).When resonance stabilization does not exist, the selectivity of cracking is reversed as being conducive to isomer 5.Also noteworthy is that, the formation as 1 and 2 shows, therefore silylation reactive is reversible under typical reaction conditions.After the possibility of illustration tool challenging 4-O-5 xylogen model 8 and 11, this method is with containing six C arthe oligo-ether 14 of-O key is tested (scheme 2, illustration D).Notably, at 165 DEG C, achieve the Quantitative yield of 14 in sym-trimethylbenzene and obtain phenol, benzene, Resorcinol and other unidentified products, every aryl oxide key has the silane of only 0.5 equivalent.
In scheme 2, compound 1 to 7 refers to the corresponding compound described in embodiment 5.9.
Embodiment 5.12: about the experiment of some additive on the impact of the cracking of diphenylene-oxide
In other experiment, Et 3the reactivity of SiH is tested in the presence of various additives thus is attempted illustrating the mechanism of reaction.In following table 4, result is shown.In product 2-7, none is identified.
Embodiment 5.13: the experiment using benzylic ether
Experiment uses the general procedure described in embodiment 3 to carry out benzylic ether.Unexpectedly, method is shown the complete deoxidation that can cause these xylogen model matrix.Such reactivity is seemingly unprecedented in state of the art homogeneous system, even if at high temperature.
Embodiment 5.14: the experiment using C-N and C-S heteroaryl compound
Experiment also uses C-N and C-S heteroaryl compound to carry out.When comprising the compound of C-N key, reactivity seems similar in appearance to the reactivity seen for C-O key, and according to reasonably expecting, the method for the wide region of the latter will cause the similar reactivity in the former:
When comprising the compound of C-S compound, method seems usually to cause the complete desulfurization of molecule.This species diversity reactive can reflect the difference (comparing the C-X dissociation energy of bond in phenol (111), aniline (104) and thiophenol (85, all in kcal/mol)) of C-O key, bond energy between C-N key and C-S key.Concerned is especially the dibenzothiophene desulfurization under relatively mild conditions of being evenly obstructed.Single C-S product is not detected in these transform:
(unidentified products, except not observing except Ar-S by GC-MS; Do not observe RS-H by NMR)
As will be apparent to those skilled in the art, many modifications and variations form of the present invention is possible according to these instructions, and has been susceptible to this type of all modifications and variations forms accordingly.Such as, except embodiment described herein, the present invention's imagination and be claimedly derived from those inventions of the combination of the feature of the present invention quoted herein and supplement those of the prior art reference quoted of feature of the present invention.Similarly, will understand, any described material, feature or goods can use with any other material, feature or article combination, and this type of combination is considered within the scope of the invention.
For all objects, the disclosure of each patent that is that quote in this document or that describe, patent application and publication is respective by reference to be thus incorporated to herein with its entirety.

Claims (60)

1. one kind for reducing the chemical system of C-O key, C-N key and C-S key, described system comprises the mixture of (a) at least one organosilane and (b) at least one highly basic, described system substantially without transistion metal compound, and described system optionally comprise at least one molecular hydrogen donor compound, molecular hydrogen or the two.
2. system as claimed in claim 1, also comprise at least one molecular hydrogen donor compound, hydrogen or the two.
3. system as claimed in claim 1, described system can make C-O key, C-N key or C-S key reductive cleavage.
4. system as claimed in claim 3, described system can make the C-O key of aromatics, C-N key or C-S key reductive cleavage.
5. system as claimed in claim 1, wherein said C-O key, C-N key or C-S key are outside ring for aromatic moieties.
6. system as claimed in claim 1, wherein said C-O key, C-N key or C-S key are inner ring for aromatic moieties.
7. system as claimed in claim 1, described system can make aliphatic C-O key, C-N key or C-S key reductive cleavage.
8. system as claimed in claim 1, described system is both anhydrous, oxygen or water and oxygen substantially.
9. system, the wherein organosilane of at least one organosilane contained (I) or formula (II) as claimed in claim 1:
(R) 4-mSi(H) m(I)R—[—SiH(R)-O—] n—R (II)
Wherein: m is 1,2 or 3;
N is 10 to 100; And
R is the C optionally replaced independently 1-12alkyl or assorted alkyl, C 5-20aryl or heteroaryl, C 6-30alkaryl or assorted alkaryl, C 6-30aralkyl or heteroaralkyl ,-O-C 1-12alkyl or assorted alkyl ,-O-C 5-20aryl or heteroaryl ,-O-C 6-30alkaryl or assorted alkaryl ,-O-C 6-30aralkyl or heteroaralkyl, and if be substituted, so substituting group can be phosphonate radical, phosphoryl, phosphinyl, phosphino-, sulfonate radical, C 1-C 20alkyl alkylthio base, C 5-C 20sulfur alkyl aryl, C 1-C 20alkyl sulphonyl, C 5-C 20aryl sulfonyl, C 1-C 20alkyl sulphinyl, C 5-C 20aryl sulfonyl kia, sulfonamido, amino, amido, imino-, nitro, nitroso-group, hydroxyl, C 1-C 20alkoxyl group, C 5-C 20aryloxy, C 2-C 20alkoxy carbonyl, C 5-C 20aryloxycarbonyl, carboxyl, carboxylate radical, sulfydryl, formyl radical, C 1-C 20thioesters, cyano group, cyanate radical, thiocyanate radical, isocyanic ester, isothiocyanic acid ester, formamyl, epoxy group(ing), styryl, silyl, silyloxy, silylation, siloxanes azanyl, borate, boryl or halogen or metallic group or containing metalloid group; wherein said metalloid is Sn or Ge, and wherein said substituting group can optionally to comprising the insoluble of aluminum oxide, silicon-dioxide or carbon or sl. sol. supporting dielectric provides link.
10. system as claimed in claim 9, wherein said organosilane is (R) 3siH, wherein R is C 1-6alkyl.
11. systems as claimed in claim 1, wherein said at least one highly basic comprises hydride or the alkoxide of basic metal or basic metal.
12. systems as claimed in claim 11, wherein said at least one highly basic comprises the hydride of basic metal or basic metal.
13. systems as claimed in claim 12, wherein said at least one highly basic comprises hydrolith or potassium hydride KH.
14. systems as claimed in claim 11, wherein said at least one highly basic comprises the alkoxide of basic metal or basic metal.
15. systems as claimed in claim 14, wherein said at least one alkoxide comprises C 1-12straight chain or the moieties of side chain or C 5-10the part of aromatics or heteroaromatic.
16. systems as claimed in claim 15, wherein said at least one alkoxide comprises methylate, ethylate, propylate, butanolate or 2-ethyl-hexanol salt.
17. systems as claimed in claim 11, the hydride of wherein said basic metal or basic metal or alkoxide base are the alkoxide of potassium or caesium.
18. systems as claimed in claim 1, wherein said organosilane is triethyl silicane and described highly basic is potassium tert.-butoxide.
19. systems as claimed in claim 1, wherein said organosilane and described at least one highly basic jointly exist with the mol ratio in from about 20:1 to the scope of about 1:2 relative to each other.
20. systems as claimed in claim 1, also include organic compounds, and described compound is both solvent, matrix or solvent and matrix.
21. systems as claimed in claim 20, wherein said organic compound is organic solvent, and described organic solvent has at one atm from the boiling point in the scope of about 25 DEG C to about 450 DEG C.
22. systems as claimed in claim 20, wherein said organic compound is containing aerobic, nitrogen, sulphur or its organic substrate combined.
23. systems as claimed in claim 22, wherein said organic substrate is comprised in biomass (such as xylogen, sugar), biomass liquefying thing, biological pyrolysis oil, black liquor, coal, gelatin liquefaction thing, Sweet natural gas or petroleum technology stream.
24. systems as claimed in claim 1, wherein said transistion metal compound exists with the 10ppm that is less than of the weight relative to total system.
25. systems as claimed in claim 1, wherein said hydrogen donor compound comprises 1，3-cyclohexadiene, 1，4-cyclohexadiene, 1,2-cyclohexadiene, 1，4-cyclohexadiene, 1,2-dihydronaphthalene, Isosorbide-5-Nitrae-dihydronaphthalene, 1,2-dihydroquinoline, 3,4-dihydroquinoline, 9,10-dihydroanthracenes or tetralin.
26. 1 kinds of methods of reducing the C-X key in organic substrate, wherein X is O, N or S, described method comprises: be enough to reduce a certain amount of described matrix described C-X key at least partially condition under, make the described matrix comprising at least one C-O key, C-N key or C-S key of described amount and comprise the chemical system of (a) at least one organosilane with the mixture of (b) at least one highly basic and contact; Wherein
Described chemical system is substantially without transistion metal compound; Described organic substrate comprises aromatic fractions; And described chemical system optionally comprise at least one molecular hydrogen donor compound, molecular hydrogen or the two.
27. methods as claimed in claim 26, also comprise at least one molecular hydrogen donor compound, hydrogen or the two.
28. methods as claimed in claim 26, wherein said organic substrate comprises at least one C-O key, and optionally comprises both at least one C-N key, C-S key or C-N key and C-S key.
29. methods as claimed in claim 26, wherein said organic substrate comprises at least one C-N key, and optionally comprises both at least one C-O key, C-S key or C-O key and C-S key.
30. methods as claimed in claim 26, wherein said organic substrate comprises at least one C-S key, and optionally comprises both at least one C-O key, C-N key or C-O key and C-N key.
31. methods as claimed in claim 26, also comprise at least one molecular hydrogen donor compound, molecular hydrogen itself or the two.
32. methods as claimed in claim 26, at least one in wherein said C-O key, C-N key or C-S key is the C-O key of aromatics, C-N key or C-S key.
33. methods as claimed in claim 32, at least one in wherein said C-O key, C-N key or C-S key is outside ring for aromatic moieties.
34. methods as claimed in claim 32, at least one in wherein said C-O key, C-N key or C-S key is inner ring for aromatic moieties.
35. methods as claimed in claim 26, wherein said matrix comprises phenyl ether, aniline, diphenyl sulfide, naphthyl ether, naphthylamines or the naphthalene polysulfide moiety or its combination that optionally replace.
36. methods as claimed in claim 26, wherein said matrix comprises furans, pyrroles, thiophene, cumarone, benzopyrrole, thionaphthene, 2,3-Dihydrobenzofuranes, xanthene, 2,3-dihydrobenzo pyrroles, 2,3-dihydrobenzo thiophene, diphenylene-oxide, dibenzopyrrole, dibenzothiophene or the diphenylene-oxide be obstructed, dibenzopyrrole or dibenzothiophene part.
37. methods as claimed in claim 26, at least one in wherein said C-O key, C-N key or C-S key is aliphatic C-O key, C-N key or C-S key.
38. methods as claimed in claim 26, described method is both anhydrous, oxygen or water and oxygen substantially.
39. methods as claimed in claim 26, the wherein organosilane of at least one organosilane contained (I) or formula (II):
(R) 4-mSi(H) m(I)R—[—SiH(R)-O—] n—R (II)
Wherein m is 1,2 or 3;
N is 10 to 100; And
R is the C optionally replaced independently 1-12alkyl or assorted alkyl, C 5-20aryl or heteroaryl, C 6-30alkaryl or assorted alkaryl, C 6-30aralkyl or heteroaralkyl ,-O-C 1-12alkyl or assorted alkyl ,-O-C 5-20aryl or heteroaryl ,-O-C 6-30alkaryl or assorted alkaryl ,-O-C 6-30aralkyl or heteroaralkyl, and if be substituted, so substituting group can be phosphonate radical, phosphoryl, phosphinyl, phosphino-, sulfonate radical, C 1-C 20alkyl alkylthio base, C 5-C 20sulfur alkyl aryl, C 1-C 20alkyl sulphonyl, C 5-C 20aryl sulfonyl, C 1-C 20alkyl sulphinyl, C 5-C 20aryl sulfonyl kia, sulfonamido, amino, amido, imino-, nitro, nitroso-group, hydroxyl, C 1-C 20alkoxyl group, C 5-C 20aryloxy, C 2-C 20alkoxy carbonyl, C 5-C 20aryloxycarbonyl, carboxyl, carboxylate radical, sulfydryl, formyl radical, C 1-C 20thioesters, cyano group, cyanate radical, thiocyanate radical, isocyanic ester, isothiocyanic acid ester, formamyl, epoxy group(ing), styryl, silyl, silyloxy, silylation, siloxanes azanyl, borate, boryl or halogen or metallic group or containing metalloid group; wherein said metalloid is Sn or Ge, and wherein said substituting group can optionally to comprising the insoluble of aluminum oxide, silicon-dioxide or carbon or sl. sol. supporting dielectric provides link.
40. methods as claimed in claim 39, wherein said organosilane is (R) 3siH, wherein R is C 1-6alkyl.
41. methods as claimed in claim 26, wherein said at least one highly basic comprises hydride or the alkoxide of basic metal or basic metal.
42. methods as claimed in claim 26, wherein said at least one highly basic comprises the hydride of basic metal or basic metal.
43. methods as claimed in claim 42, wherein said at least one highly basic comprises hydrolith or potassium hydride KH.
44. methods as claimed in claim 26, wherein said at least one highly basic comprises the alkoxide of basic metal or basic metal.
45. methods as claimed in claim 44, wherein said at least one alkoxide comprises C 1-12straight chain or the moieties of side chain or C 5-10the part of aromatics or heteroaromatic.
46. methods as claimed in claim 45, wherein said at least one alkoxide comprises methylate, ethylate, propylate, butanolate or 2-ethyl-hexanol salt.
47. methods as claimed in claim 41, the hydride of wherein said basic metal or basic metal or alkoxide base are the alkoxide of potassium or caesium.
48. methods as claimed in claim 26, wherein said organosilane is triethyl silicane and described highly basic is potassium tert.-butoxide.
49. methods as claimed in claim 26, wherein said organosilane and described at least one highly basic jointly exist with the mol ratio in from about 20:1 to the scope of about 1:2 relative to each other.
50. methods as claimed in claim 26, the C-X key in wherein said organosilane and described matrix is to exist from about 1:2 to the ratio of about 10:1.
51. methods as claimed in claim 26, the C-X key in wherein said highly basic and described matrix is to exist from about 1:2 to the scope of about 10:1.
52. methods as claimed in claim 26, wherein said organosilane exists to be enough to the amount of serving as the solvent of described method.
53. methods as claimed in claim 26, also comprise organic solvent.
54. methods as claimed in claim 53, described organic solvent has at one atm from the boiling point in the scope of about 25 DEG C to about 450 DEG C.
55. methods as claimed in claim 26, described method comprises and is heated to described organic substrate and described chemical system from the temperature in the scope of about 25 DEG C to about 450 DEG C.
56. methods as claimed in claim 26, wherein said transistion metal compound exists with the 10ppm that is less than of the weight relative to total system.
57. methods as claimed in claim 26, wherein said hydrogen donor compound comprises 1，3-cyclohexadiene, 1，4-cyclohexadiene, 1,2-cyclohexadiene, 1，4-cyclohexadiene, 1,2-dihydronaphthalene, Isosorbide-5-Nitrae-dihydronaphthalene, 1,2-dihydroquinoline, 3,4-dihydroquinoline, 9,10-dihydroanthracenes or tetralin.
58. methods as claimed in claim 26, wherein said organic substrate is comprised in biomass (such as xylogen, sugar), biomass liquefying thing, biological pyrolysis oil, black liquor, coal, gelatin liquefaction thing, Sweet natural gas or petroleum technology stream.
59. methods as claimed in claim 26, wherein said method is carried out in biomass (such as xylogen, sugar), biomass liquefying thing, biological pyrolysis oil, black liquor, coal, gelatin liquefaction thing, Sweet natural gas or petroleum technology stream.
60. methods as claimed in claim 26, wherein said method produces such product, in the product in described C-X key at least one with scope from relative to the amount be primitively present in described matrix compounds about 40% to 100% amount be reduced.
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